Electrophile-Mediated Reactions of Functionalized Propargylic Substrates

FULL PAPER

DOI: 10.1002/ejoc.201501063

[a]

ˇ

Aurelija Urbanaite˙, Mantas Jonusis, Rita Buksnaitiene˙, Simonas Balkaitis, and

[a]

ˇ

Inga Cikotiene˙*

Keywords: Alkynes / Electrophilic addition / Cyclization / Nitrogen heterocycles / Sulfur heterocycles / Regioselectivity

Metal-free halogen, chalcogen, or oxocarbenium ion medi-

ated yne-carbonyl or yne-thioxo transformations of a range

of N- and O-propargylic compounds have been studied. This

investigation has led to the development of a mild, economic,

and effective method for the synthesis of functionalized 4H-

1,3-oxazines, 4H-1,3-thiazines, 4,5-dihydrothiazoles, and α-

substituted enones. The structure of the propargylic substrate

and the nature of electrophile influence both the outcome

and regioselectivity of processes.

These preliminary findings prompted us to study the scope

of electrophile-mediated transformations of functionally

substituted propargylic substrates. In this work, we present

the results of our recent and more detailed investigations.

Introduction

In the past decade an explosive increase of interest in

electrophile-mediated cyclizations of alkynes has taken

place.^[1]These methodologies have become an original field

of carbo- and heterocycle synthesis and have enabled the

formation of halogen- or chalcogen-substituted com-

pounds. The obtained materials are suitable for further syn-

thetic transformations. Electrophilic cyclizations of alkynes

may be defined as processes that involve addition of an elec-

trophilic source to sp-carbon centers and subsequent for-

mation of cyclic compounds through attack of neighboring

nucleophilic functionality through either endo or exo

modes. The mode of cyclization normally depends on chain

length, substitution pattern on the chain, and on the elec-

trophile employed. Functionalized propargylic substrates

are a specific class of alkynes with attractive chemical prop-

erties. It is known that these materials can undergo a

number of skeletal rearrangements and cyclization reactions

and these processes are usually mediated by activation of

the triple bond by transition-metal salts.^[2]Despite the fact

that electrophilic cyclization reactions of alkynes bearing an

internal nucleophile have emerged as a very efficient process

to obtain a variety of prefunctionalized compounds, this

type of activation is still not common for functionalized

Results and Discussion

As starting propargylic substrates we chose six classes of

compounds: amides 1, carbamates 2 and 5, ureas 3, thio-

ureas 4, and esters 6. We utilized known methods for the

preparation of these compounds. The strategy of their syn-

thesis is presented in the Supporting Information. Struc-

tures of the starting materials are shown in Figure 1.

Figure 1. Structures of the starting materials. 1: R = 4-MeOC₆H₄

(a); R = 4-EtOC₆H₄(b); R = 3,4-(MeO)₂C₆H₃(c); R = 3,4,5-(MeO)₃-

propargylic substrates.^[3]Recently, we have found that elec- C₆H₂(d); R = 4-MeC₆H₄(e); R = Ph (f); R = 4-ClC₆H₄(g); R =

4-O₂NC₆H₄(h); R = H (i). 2: R = 4-MeOC₆H₄(a); R = 3,4-(MeO)₂-

trophilic reagents (iodine or N-iodo succinimide, aldehydes

C₆H₃(b); R = 3,4-(OCH₂O)C₆H₃(c); R = 4-MeC₆H₄(d); R = Ph

or oxocarbenium ions) can be used to induce 1,3-acyloxy

(e); R = 4-ClC₆H₄(f); R = 4-O₂NC₆H₄(g); R = H (h). 3: R = 4-

shifts in propargylic esters.^[4]Moreover, at the beginning of

MeOC₆H₄; RЈ = Ts (a); R = 4-MeOC₆H₄; RЈ = Ph (b); R = 4-

2015, we presented an electrophilic cyclization of N-(3-aryl-

MeOC₆H₄; RЈ = Bn (c); R = 3,4-(MeO)₂C₆H₃; RЈ = Ts (d); R =

4-MeC₆H₄; RЈ = Bn (e); R = 4-MeC₆H₄; RЈ = Ts (f); R = Ph_;RЈ

= Ts (g); R = 4-ClC₆H₄; RЈ = Ts (h); R = H; RЈ = Ts (i); R = H;

RЈ = Ph (j); R = H; RЈ = Bn (k). 4: R = 4-MeOC₆H₄(a); R = 4-

ClC₆H₄(b); R = Ph (c); R = H (d). 5: Ar = 4-MeOC₆H₄; R = Ts

(a); Ar = 4-MeOC₆H₄; R = Bn (b). 6: Ar = 4-MeOC₆H₄(a); Ar =

Ph (b).

prop-2-ynyl)amides to functionalized 4H-1,3-oxazines.^[5]

[a] Department of Organic Chemistry, Faculty of Chemistry,

Vilnius University,

Naugarduko 24, 03225 Vilnius, Lithuania

E-mail: inga.cikotiene@chf.vu.lt

http://web.vu.lt/chf/i.cikotiene

With synthesized propargylic substrates in hand, we ex-

plored the scope of electrophile-mediated reactions. For the

Supporting Information for this article is available on the

WWW under http://dx.doi.org/10.1002/ejoc.201501063.

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Scheme 1. General outcomes of electrophile-mediated reactions of propargylic substrates.

chosen model substrates and electrophile sources, we per- smooth and chromatographically clean transformations

formed detailed optimization processes, including an inves- with N-iodosuccinimide (NIS) in CH₂Cl₂at ambient tem-

tigation of solvent, temperature, base, and stoichiometry; perature, other substrates required some modification of the

the results of optimization study are presented in the Sup- procedure (see Table S1). Thus, two equivalents of molec-

porting Information (Table S1). With appropriate reactions ular iodine in either CH₂Cl₂or acetonitrile at 0 °C were the

conditions for halogen-, chalcogen-, and oxocarbenium ion best conditions for iodocyclizations of carbamates 2 and

mediated reactions established, we synthesized a wide range ureas 3. Ester 6a participated in competitive electrophilic

of functionalized heterocyclic compounds and α-substituted addition reaction during NIS or molecular iodine^[4a]medi-

enones. The results are presented in chapters 1–3 together ated transformation and therefore the yield of isolated iod-

with some concluding remarks on the reactions, which are inated enone 11aa was low (Table 1, entry 41). N-Bromo-

presented in chapter 4. The general trends of reactivity of succinimide (NBS) was not efficient for such transforma-

the studied propargylic substrates are shown in Scheme 1.

tions. Whereas carbamates 2 formed six-membered bromo-

derivatives 8 in low yields (entries 11, 13, 16, 18, and 20),

NBS-mediated reactions of amides 1, ureas 3, carbamates

5, and esters 6 were problematic and resulted in low conver-

sions of the starting materials (data not shown). N-Chloro-

succinimide was completely ineffective.

1. Halogen-Mediated Reaction of Propargylic Substrates

Reactions between propargylic substrates and iodine

electrophile sources proceeded well and resulted in the for-

mation of iodo-substituted 4H-1,3-oxazines 7–9, 4H-1,3-

As seen from Table 1, substrates bearing an electron-rich

thiazines 10, and α-iodoenones 11 as main reactions prod- aryl group next to the triple bonds (amides 1a–f, carb-

ucts. Whereas amides 1 and carbamates 5 underwent amates 2a–f and 5a,b, ureas 3a,c–g, and ester 6a; entries 1–

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Electrophile-Mediated Reactions of Propargylic Derivatives

Table 1. Data on the halogen-mediated reactions of substrates.

[a] Aryl(2-phenyloxazol-5-yl)methanones 21ga and 21ha, and 2-phenyloxazole-5-carbaldehyde 21ia were isolated. [b] The same compound

was obtained by using molecular iodine in CH₂Cl₂at room temp. [c] 6,6Ј-Diaryl-5,5Ј-dibromo-3Ј,4Ј-dihydro-2ЈH-3,4Ј-bi(1,3-oxazine)-

2,2Ј(4H)-diones 22 formed as minor products.

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6, 10–18, 24, 26, 28, 29, and 39–41) underwent regioselec- iodonium-mediated reaction, two possible pathways are

tive and dominant 6-endo-dig processes under halonium ion possible: 5-exo-dig cyclization reaction occurs after forma-

mediated reactions. Iodine-mediated reactions of starting tion of a CT complex and competing 6-endo-dig cyclization

materials with electron-poor aryl groups next to the triple takes place after conversion of the CT complex into open

bond (1g, 1h, and 2g) proceeded slowly and ineffectively. iodovinyl (I) or bridged iodirenium^[7](II) ions (Scheme 2).

Thus, N-[3-(4-chloro or 4-nitrophenyl)prop-2-ynyl]benz-

amides 1g and 1h formed a mixture of six-membered and

2. Phenyl Hypochloroselenoite Mediated Reaction of

Propargylic Substrates

five-membered heterocyclic products 7, 12, and 21 in NIS-

mediated cyclizations (entries 7 and 8). By using starting

tert-butyl 3-(4-nitrophenyl)prop-2-ynylcarbamate 2g (en-

tries 21 and 22) or 1-substituted-3-(prop-2-ynyl)ureas 3j and

3k (entries 31 and 32), regioselective formation of 5-exo-

dig cyclization products in halogen-mediated reactions was

observed. In some cases, terminal propargylic substrates in

halogen-mediated reactions formed mixtures of isoxazole

ring containing compounds and products of electrophilic

addition reactions (entries 9, 23 and 30).

After investigation of halogen-mediated reactions, we

turned our attention to phenyl hypochloroselenoite as a

source of chalcogen-electrophile. It should be noted that the

presence of base (tBuOK for amides 1 and K₃PO₄·H₂O for

carbamates 2) is required for successful reactions (see the

Supporting information, Table S1). In contrast, ureas 3 and

thioureas 4 underwent phenyl hypochloroselenoite-trig-

gered base-independent and selective reactions.

In contrast to the chemistry of amides, carbamates and

ureas, iodine-mediated cyclizations of electron-rich thio-

ureas 4 were unselective (entries 33 and 36) and we were

surprised when these starting materials underwent ring-clo-

sure through the 5-exo-dig mode exclusively during halo-

gen-mediated cyclizations (entries 34, 35, and 37). The

structures of all six- and five-membered cyclic products

were established based on NMR spectroscopic analysis. In

particular, after assignment of carbon signals by using a

combination of COSY, HSQC, and HMBC experiments,

the analysis of HMBC spectra of all cyclic products was

performed. In the case of compounds 15, the presenting

cross-peaks between ortho protons of C(6)-Ar and C_sp2-Br

or C_sp2-I nuclei indicated a five-membered core. In the

HMBC spectra of six-membered cyclic compounds 10,

cross-peaks between ortho protons of C(6)-Ar and C_sp2-Br

or C_sp2-I nuclei were absent.

It is known that because of the large size and ready po-

larization, sulfur is a stronger nucleophile than oxygen;

therefore, cyclizations of thioureas 4 proceeded more read-

ily than analogous reactions of amides 1, carbamates 2, and

ureas 3. We presume that in bromine-mediated cyclizations

of thioureas 4, nucleophilic attack occurs just after the ini-

tial formation of the charge-transfer complex between the

bromonium ion and the triple bond.^[6]The carbon–carbon

triple bond in charge transfer (CT) complexes between alk-

yne and halogen remains linear; therefore, nucleophilic

sulfur attack occurs through the 5-exo-dig mode. From

the results obtained, we hypothesized that during the

Propargylic amides 1 and Boc-protected propargylic

amines 2 during reactions with phenyl hypochloroselenoite

underwent smooth 6-endo-dig cyclizations. However, both

classes of these substrates also underwent side addition re-

actions and (E)-N-[3-aryl-3-chloro-2-(phenylselanyl)allyl]-

benzamides 16 (Table 2, entries 1–6) or (E)-tert-butyl 3-

aryl-3-chloro-2-(phenylselanyl)allylcarbamates 17 formed

(entries 10–14). When starting compounds 1i and 2h, with

terminal alkyne groups, were used, the regioselectivity of

the addition reaction differed and compounds 16Јib and

17Јhc were isolated (entries 9 and 15).

Ureas 3 and thioureas 4, having electron-rich aryl groups

next to the triple bond, underwent regioselective phenyl

hypochloroselenoite triggered base-free 6-endo-dig cycliza-

tions, and electrophilic addition did not take place (Table 2,

entries 16, 17, 19–21, and 25–27). However, terminal prop-

argylic ureas 3j and 3k, and thiourea 4d in the reaction with

phenyl hypochloroselenoite formed 4,5-dihydrothiazoles 14

and 15 through 5-exo-dig cyclization (entries 23, 24, and

28). The exception was 4-methyl-N-(prop-2-ynylcarbamoyl)-

benzenesulfonamide (3i), which did not participate in

cyclization reaction and, after treatment with the reagent,

converted

into

(E)-N-[2-chloro-3-(phenylselanyl)allyl-

carbamoyl]-4-methylbenzenesulfonamide (18Јib; entry 22).

Unfortunately, carbamate 5a and ester 6a, having O-

propargyl functionality, did not undergo the expected re-

arrangement reaction with phenyl hypochloroselenoite, and

high-yielding electrophilic addition reaction took place

(Table 2, entries 29 and 30).

3. Oxocarbenium Ion Mediated Reaction of Propargylic

Substrates

Another group of electrophiles that we studied were oxo-

carbenium ions formed from acetals through Lewis acid

mediation. The data obtained are presented in Table 3 and

Table 4.

Reactions between 1-methoxyisochroman and proparg-

ylic substrates proceeded smoothly and regioselectively.

However, the activation of the triple bond by an electron-

Scheme 2. Possible mechanisms of halogen-mediated 5-exo-dig and

6-endo-dig cyclizations of thioureas 4.

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Electrophile-Mediated Reactions of Propargylic Derivatives

Table 2. Data for the phenyl hypochloroselenoite mediated reactions of substrates.

rich aryl group was required for successful 6-endo-dig reac- selective reactions of 3c were observed for halogen- and

tion. Thus, functionalized aryl-substituted propargylic phenyl hypochloroselenoite triggered reactions (Table 1, en-

amides 1, carbamates 2, ureas 3, or thioureas 4 in the pres- tries 25 and 27, and Table 2, entry 18).

ent reaction formed 5-(isochroman-1-yl)-4H-1,3-oxazines

Esters 6 and carbamates 5 underwent our previously re-

or 5-(isochroman-1-yl)-4H-1,3-thiazines in good yields ported^[4a]6-endo-dig rearrangement reactions to 1-aryl-2-

(Table 3, entries 1–6, 9–13, 16, 18–21, and 23–25). Com- (isochroman-1-yl)-1prop-2-en-1-ones 11 (Table 3, en-

pounds bearing either a terminal propargylic fragment or tries 27–30). It should be noted that parallel reactions be-

an electron-poor aromatic ring were not active towards 3,4- tween starting materials and Lewis acids without acetals

dihydroisochromenylium ion mediated reactions (entries 7, were also performed. In almost all cases, slow decomposi-

8, 14, 15, 22, 26). 1-Benzyl-3-[3-(4-methoxyphenyl)prop-2- tion of the starting materials occurred.

ynyl]urea (3c) in reaction with 1-methoxyisochroman

Reactions between propargylic amides 1 and acyclic acet-

formed a mixture of inseparable products (entry 17) and we als under the optimized conditions (Table S1) led to the for-

suppose that this is dictated by the two nucleophilic atoms mation of predominantly six-membered products 7, with

(carbonyl oxygen and the nitrogen of the benzylamino frag- minor amounts of enones 23 and 24 (Table 4, entries 1–8).

ment) presenting in the functional group. Analogous un- After the activation of acetals by oxophilic Lewis acids

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Table 3. Data for the 3,4-dihydroisochromenylium ion mediated reactions of substrates.

(BF₃·OEt₂or TMSOTf) the formation of electrophilic oxo- 4. Factors Affecting the Outcome of Electrophile Mediated

carbenium ions occur. After addition of the electrophile to Reactions of Propargylic Substrates

the triple bond of amide 1, two possible intramolecular re-

actions of the resulting ion I can then take place concur-

Some general remarks on the investigated reactions can

rently. The desired reaction (Route a) is 6-endo-dig O- be made. First, almost all investigated propargylic sub-

nucleophilic attack resulting in cyclization products. The strates undergo cyclization or rearrangement reactions and

side reaction is ring closure to four-membered 1,2-dihy- these processes usually dominate over simple electrophilic

drooxetium intermediate IV and subsequent cycloreversion addition reactions. Second, the outcomes of the studied re-

to enones^[9](Scheme 3).

actions depend on three main factors: electron density on

In contrast, N-(3-arylprop-2-ynylcarbamothioyl)benz- the alkyne, the electrophile used, and the structure of the

amides 4 reacted with acyclic acetals selectively and formed functional nucleophilic group. Thus, the rates of the reac-

N-{5-[alkoxy(aryl)methyl]-6-aryl-4H-1,3-thiazin-2-yl}benz- tions as well as the regioselectivity of the processes depend

amides 10 in good yield (Table 4, entries 11–18).

strongly on the substituent next to the triple bond. Reac-

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Electrophile-Mediated Reactions of Propargylic Derivatives

Table 4. Data for arylideneoxonium ion mediated reactions of substrates.

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Scheme 3. Intermediates in reactions between propargylic amides

with acyclic oxocarbenium electrophiles.

tions of substrates bearing electron-donating aryl groups

proceeded smoothly and usually in selective 6-endo-dig

mode. These observations could be logically explained by

participation of the electron-donating aryl group in stabili-

zation of the intermediate vinylic carbocation I formed dur-

ing the first stage of the electrophilic activation (Scheme 4).

Starting materials with electron-poor aryl groups (4-

ClC₆H₄-, 4-O₂NC₆H₄-) next to the triple bond, or terminal

Scheme 5. Stabilization of vinylic carbocation I and subsequent 5-

exo-dig processes of electron-poor propargylic substrates.

Undesired electrophilic additions can take place during

propargylic substrates were not so active in electrophile-me- halonium- or phenyl hypochloroselenoite mediated reac-

diated reactions. These materials required prolonged reac- tions, because nucleophilic anions are present in the media.

tions times for full conversion, and yields of isolated prod- Thus, during activation of the triple bond by Hal⁺or PhSe⁺

ucts were not high. Moreover, usually a change of cycliza- ions, the formation of vinylic carbocations I can take place.

tion mode from 6-endo into 5-exo was observed. The dif- The open-chain vinylic carbocations I can be in equilibrium

ferent regioselectivity can be explained by participation of with haloirenium or selenirenium ions II, which is consis-

CH₂FG groups in the inductive stabilization of the neigh- tent with recent experimental and theoretical studies.^[7,8]

boring cationic center of the formed vinylic carbocation V Neither open-chain nor cyclic antiaromatic ions are very

(Scheme 5).

stable and the subsequent nucleophilic attack of the neigh-

Scheme 4. Stabilization of vinylic carbocation I and subsequent 6-endo-dig processes of electron-rich propargylic substrates.

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Electrophile-Mediated Reactions of Propargylic Derivatives

boring functional group or halogen counterion takes place alized enones. We expect that the presented processes will

readily. We suppose that the dominant process is dictated find applications in the synthesis of complex structures.

by the nucleophilicity of the internal functional group and

by the stability of cyclic intermediates III. When the nucleo-

Experimental Section

philicity of the internal functional group is high (as for

ureas 3 and thioureas 4), usually an exclusive cyclization

process occurs. In the opposite case, the halogen counterion

acts as a nucleophile and formation of side addition prod-

ucts 16–20 takes place (Scheme 4). Notably, the stability of

the six-membered cationic intermediates III depends on the

type of heterocyclic cation. Thus, 4H-1,3-dioxin-2-ylium

ions (X = Y = O) seem to be less stable than 4H-1,3-oxazin-

3-ium (X = NH; Y = O) or 4H-1,3-thiazin-3-ium (X = NH;

Y = S) ions. Therefore, electrophilic addition reactions of

O-propargyl derivatives 5 and 6 can dominate in halonium

and phenyl chloroselenoite mediated processes (Table 1, en-

try 41 and Table 2, entries 29 and 30).

1

General Information: IR spectra were recorded from KBr discs. H

and ¹³C NMR spectra were recorded at 400 MHz in [D]chloroform

or [D₆]dimethyl sulfoxide, using residual solvent signal as internal

standard. Signal multiplicity is abbreviated as: s (singlet), d (doub-

let), t (triplet), q (quartet), quint (quintet), m (multiplet). Unambig-

uous assignment of signals was made by using a combination of

NMR experiments, including COSY, HSQC, and HMBC. High-

resolution mass spectra were recorded with a Dual-ESI Q-TOF

6520 mass spectrometer with electrospray ionization. All reactions

and the purity of the synthesized compounds were monitored by

TLC using silica gel 60 F254 aluminum plates. Visualization was

accomplished under UV light and by treating the plates with vanil-

lin stain followed by heating.

Third, we observed that, in all successful cases, either the

carbonyl oxygen or the thiocarbonyl sulfur acted as nucleo-

philes during the transformations. Fourth, the data ob-

tained from these studies indicate the main difference in

electrophile-mediated reactions between compounds bear-

ing O- and N-propargyl functionality. Whereas compounds

bearing N-propargyl groups (amides 1, carbamates 2, ureas

3, and thioureas 4) underwent electrophilic cyclization reac-

tions quite easily, in the case of the corresponding O-prop-

argyl derivatives (carbamates 5 and esters 6), transforma-

tions into α-functionalized enones took place (Scheme 4).

It is worth mentioning that propargylic substrates 1h,i,

2g,h, 3k, and 4d, bearing a terminal or 4-nitrophenyl sub-

stituent, were completely unreactive towards oxocarbenium

electrophiles (Table 3, entries 8, 14, 15, 22, and 26; Table 4,

entries 9, 10, and 19). However, in contrast, reactions of

these materials with iodine or phenylhypochloroselenoite

proceeded, albeit ineffectively. This fact indicates that the

ability to form cyclic haloirenium or selenirenium ions plays

a role in the partial stabilization of vinylic carbocations.

Therefore, unactivated propargylic substrates react with

halogen- or chalcogen-based electrophiles, but do not un-

dergo oxocarbenium ion mediated transformations because

of the lack of stabilization (Scheme 5).

General Procedures for Halogen-Mediated Reactions

Method A: To a solution of 1, 5, or 6 (1 mmol) in dichloromethane

(5 mL), N-iodosuccinimide (0.25 g, 1.1 mmol) was added. The mix-

ture was stirred at room temperature.

Method B: To a cooled solution of 2 or 4 (1 mmol) in anhydrous

chloroform (5 mL) or 3 (1 mmol) in anhydrous acetonitrile (5 mL),

molecular iodine (0.51 g, 2 mmol) was added at 0 °C. The resulting

stirred solution was warmed to room temperature.

Method C: To a solution of 2 or 4 (1 mmol) in dichloromethane

(5 mL), N-bromosuccinimide (0.19 g, 1.1 mmol) was added. The

mixture was stirred at room temperature.

Isolation Procedures for All Products: When completion of the reac-

tion was determined by TLC analysis, the reaction was quenched

with aqueous sodium thiosulfate. The organic layer was separated,

washed with aqueous sodium thiosulfate (2ϫ20 mL), and then

with water (2ϫ20 mL), and dried with anhydrous Na₂SO₄. After

the evaporation of solvent under reduced pressure, the residue was

purified by flash column chromatography eluting with hexane/ethyl

acetate mixtures.

5-Iodo-6-(4-methoxyphenyl)-2-phenyl-4H-1,3-oxazine (7aa): Yield

0.28 g (72%); white solid; m.p. 119–120 °C. ¹H NMR (400 MHz,

3

CDCl₃): δ = 3.86 (s, 3 H, OCH₃), 4.56 (s, 2 H, CH₂), 6.96 (d, J =

3

8.8 Hz, 2 H, ArH), 7.40 (t, J = 7.6 Hz, 2 H, ArH), 7.48 (tt, J =

7.6, ⁴J = 2.4 Hz, 1 H, ArH), 7.63 (d, ³J = 8.8 Hz, 2 H, ArH), 7.95–

7.97 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.2

(CH₂), 55.4 (OCH₃), 69.8 (CI), 113.6 (ArC), 126.6 (ArC), 127.4

(ArC), 128.4 (ArC), 130.5 (ArC), 131.1 (ArC), 131.7 (ArC), 147.7

(Csp²), 153.7 (Csp²), 160.6 (ArC) ppm. HRMS (ESI): m/z calcd.

for C₁₇H₁₅INO₂[M + H] 392.0142; found 392.0148.

Conclusions

We have shown that substrates with various N- and O-

propargil moieties can undergo electrophile-triggered reac-

tions without the need for transition-metal catalysis. The

scope and limitations of these processes were investigated

by using a broad range of substrates. Based on our findings,

efficient synthetic protocols for functionalized 4H-1,3-ox-

azines, 4H-1,3-thiazines, and 4,5-dihydrothiazoles have been

developed. These methodologies permit one-step formation

of heterocycle and simultaneous installation of halogen,

chalcogen, or benzyl ether functionality onto the ring.

Moreover, we proved that whereas propargylamine deriva-

tives undergo electrophilic cyclization reactions, materials

6-(4-Ethoxyphenyl)-5-iodo-2-phenyl-4H-1,3-oxazine (7ba): Yield

0.24 g (58%); white solid; m.p. 108–109 °C. ¹H NMR (400 MHz,

3

CDCl₃): δ = 1.44 (t, J = 7.2 Hz, 3 H, OCH₂CH₃), 4.08 (q, J =

3

7.2 Hz, 2 H, OCH₂CH₃), 4.55 (s, 2 H, CH₂), 6.94 (d, J = 8.8 Hz,

2 H, ArH), 7.39 (t, J = 8.0 Hz, 2 H, ArH), 7.46 (tt, J = 7.6, J =

2.4 Hz, 1 H, ArH), 7.61 (d, J = 8.8 Hz, 2 H, ArH), 7.92–7.94 (m,

3

4

3

2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 14.9 (CH₃),

55.5 (CH₂), 63.6 (OCH₂CH₃), 69.9 (CI), 114.0 (ArC), 126.6 (ArC),

127.3 (ArC), 128.4 (ArC), 130.5 (ArC), 131.3 (ArC), 131.7 (ArC),

147.8 (Csp²), 153.0 (Csp²), 159.9 (ArC) ppm. HRMS (ESI): m/z

calcd. for C₁₈H₁₇INO₂[M + H] 406.0298; found 406.0294.

6-(3,4-Dimethoxyphenyl)-5-iodo-2-phenyl-4H-1,3-oxazine

(7ca):

having a propargyloxy group can rearrange into α-function- Yield 0.22 g (52%); white solid; m.p. 147–148 °C. ¹H NMR

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7099

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

(400 MHz, CDCl₃): δ = 3.93 (s, 3 H, OCH₃), 3.93 (s, 3 H, OCH₃), 132.0 (ArC), 135.1 (ArC), 137.7 (ArC), 139.8 (ArC), 148.8 (ArC),

3

4

4.56 (s, 2 H, CH₂), 6.92 (d, J = 8.4 Hz, 1 H, ArH), 7.21 (d, J =

2.0 Hz, 1 H, ArH), 7.27 (dd, ³J = 8.6, ⁴J = 2.0 Hz, 1 H, ArH), 7.40

(t, ³J = 7.6 Hz, 2 H, ArH), 7.48 (tt, ³J = 7.6, ⁴J = 2.4 Hz, 1 H,

ArH), 7.94–7.96 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

CDCl₃): δ = 55.1 (CH₂), 56.0 (CH₃), 56.1 (CH₃), 70.0 (CI), 110.6

(ArC), 112.2 (ArC), 122.1 (ArC), 126.7 (ArC), 127.3 (ArC), 128.4

(ArC), 131.3 (ArC), 131.5 (ArC), 147.7 (Csp²), 148.4 (ArC), 150.1

(ArC), 153.4 (Csp²) ppm. HRMS (ESI): m/z calcd. for C₁₈H₁₆IN-

NaO₃[M + Na] 444.0067; found 444.0060.

164.9 (ArC), 180.0 (C=O) ppm. HRMS (ES): m/z calcd. for

C₁₆H₁₀ClNNaO₂[M + Na] 306.0298; found 306.0299.

5-Iodo-6-(4-nitrophenyl)-2-phenyl-4H-1,3-oxazine (7ha): Yield 0.1 g

(24%); white solid; m.p. 190–191 °C. ¹H NMR (400 MHz, CDCl₃):

3

δ = 4.91 (s, 2 H, CH₂), 7.46 (t, J = 7.2 Hz, 2 H, ArH), 7.56 (t, J

3

= 7.2 Hz, 1 H, ArH), 7.86 (d, J = 9.2 Hz, 2 H, ArH), 7.90–7.92

(m, 2 H, ArH), 8.23 (d, ³J = 9.2 Hz, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 65.7 (CH₂), 67.3 (CI), 123.5 (ArC), 126.2

(ArC), 128.1 (ArC), 128.9 (ArC), 130.4 (ArC), 132.6 (ArC), 144.3

(ArC), 146.7 (Csp²), 156.0 (Csp²), 163.9 (ArC) ppm. HRMS (ESI):

m/z calcd. for C₁₆H₁₂IN₂O₃[M + H] 406.9887; found 406.9889.

5-Iodo-2-phenyl-6-(3,4,5-trimethoxyphenyl)-4H-1,3-oxazine (7da):

Yield 0.27 g (60%); white solid; m.p. 184–185 °C. ¹H NMR

(400 MHz, CDCl₃): δ = 3.90 (s, 6 H, 2ϫOCH₃), 3.91 (s, 3 H,

OCH₃), 4.56 (s, 2 H, CH₂), 6.90 (s, 2 H, ArH), 7.40 (t, ³J = 8.0 Hz,

2 H, ArH), 7.49 (tt, ³J = 7.6, ⁴J = 2.4 Hz, 1 H, ArH), 7.92–7.94

(m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.4 (CH₂),

56.4 (2ϫOCH₃), 61.0 (OCH₃), 70.7 (CI), 106.6 (ArC), 127.2 (ArC),

128.4 (ArC), 129.6 (ArC), 131.4 (ArC), 131.6 (ArC), 139.2 (ArC),

147.8 (Csp²), 152.8 (Csp²), 159.9 (2ϫArC) ppm. HRMS (ESI): m/z

calcd. for C₁₉H₁₉INO₄[M + H] 452.0353; found 452.0347.

(4-Nitrophenyl)(2-phenyloxazol-5-yl)methanone (21ha): Yield 47 mg

(16 %); yellowish solid; m.p. 186–187 °C. ¹H NMR (400 MHz,

CDCl₃): δ = 7.51–7.61 (m, 3 H, ArH), 7.94 (s, 1 H, ArH), 8.15–

8.20 (m, 4 H, ArH), 8.41 (d, ³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C

NMR (100 MHz, CDCl₃): δ = 124.1 (ArC), 125.9 (ArC), 127.8

(ArC), 129.3 (ArC), 130.1 (ArC), 132.5 (ArC), 138.8 (ArC), 141.8

(ArC), 148.6 (Csp²), 150.4 (ArC), 165.6 (Csp²), 179.5 (CO) ppm.

HRMS (ESI): m/z calcd. for C₁₆H₁₁N₂O₄[M + H] 295.0713; found

295.0713.

5-Iodo-2-phenyl-6-p-tolyl-4H-1,3-oxazine (7ea): Yield 0.22 g (58%);

white solid; m.p. 125–126 °C. ¹H NMR (400 MHz, CDCl₃): δ =

2.41 (s, 3 H, CH₃), 4.57 (s, 2 H, CH₂), 7.26 (d, J = 8.0 Hz, 2 H,

2-Phenyloxazole-5-carbaldehyde (21ia): Yield 27.7 mg (16%); solid;

3

m.p. 103–104 °C. IR (KBr): ν

= 1668 (C=O) cm^–1. ¹H NMR

˜

max

3

ArH), 7.40 (t, J = 8.0 Hz, 2 H, ArH), 7.49 (t, J = 7.6 Hz, 1 H,

ArH), 7.57 (d, ³J = 8.0 Hz, 2 H, ArH), 7.95–7.97 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.6 (CH₃), 55.1

(CH₂), 70.3 (CI), 127.5 (ArC), 128.4 (ArC), 129.0 (ArC), 131.0

(ArC), 131.3 (ArC), 131.7 (ArC), 140.0 (ArC), 147.9 (Csp²), 153.8

(Csp²) ppm. HRMS (ESI): m/z calcd. for C₁₇H₁₅INO [M + H]

376.0193; found 376.0189.

(400 MHz, CDCl₃): δ = 7.48–7.58 (m, 3 H, ArH), 7.95 (s, 1 H,

CH), 8.16–8.19 (m, 2 H, ArH), 9.81 (s, 1 H, CHO) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 126.0 (ArC), 127.8 (ArC), 129.2 (ArC),

132.4 (ArC), 139.2 (Csp²), 149.7 (Csp²), 165.6 (Csp²), 176.4

(CHO) ppm. HRMS (ESI): m/z calcd. for C₁₀H₇NNaO₂[M + Na]

196.0369; found 196.0368.

(E)-N-(2,3-Diiodoallyl)benzamide (16ia): Yield 0.16 g (41%); yel-

1

3

5-Iodo-2,6-diphenyl-4H-1,3-oxazine (7fa): Yield 0.18 g (52%); white

lowish oil. H NMR (400 MHz, CDCl₃): δ = 4.62 (d, J = 3.2 Hz,

1

3

solid; m.p. 105–106 °C. H NMR (400 MHz, CDCl₃): δ = 4.57 (s,

2 H, CH₂), 5.79 (t, J = 3.2 Hz, 1 H, CH), 7.44 (t, J = 7.6 Hz, 2

H, ArH), 7.53 (t, ³J = 7.6 Hz, 1 H, ArH), 7.94–7.97 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 47.5 (CH₂), 61.1

(HC_sp2I), 126.4 (C_sp2I), 128.2 (ArC), 128.7 (ArC), 132.3 (ArC),

157.8 (ArC), 164.2 (NHCO) ppm. HRMS (ESI): m/z calcd. for

C₉H₁₁I₂NO [M + H] 402.8930; found 402.8936.

2 H, CH₂), 7.38–7.48 (m, 6 H, ArH), 7.66–7.69 (m, 2 H, ArH),

7.93–7.95 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

55.4 (CH₂), 70.9 (CI), 127.2 (ArC), 128.2 (ArC), 128.3 (ArC), 129.1

(ArC), 129.7 (ArC), 131.3 (ArC), 131.6 (ArC), 134.4 (ArC), 148.0

(Csp²), 152.8 (Csp²) ppm. HRMS (ESI): m/z calcd. for C₁₆H₁₃INO

[M + H] 362.0036; found 362.0036.

5-Iodo-6-(4-methoxyphenyl)-3,4-dihydro-2H-1,3-oxazin-2-one (8aa):

6-(4-Chlorophenyl)-5-iodo-2-phenyl-4H-1,3-oxazine (7ga): Yield

0.08 g (20%); white solid; m.p. 122–123 °C. ¹H NMR (400 MHz,

CDCl₃): δ = 4.55 (s, 2 H, CH₂), 7.37–7.43 (m, 4 H, ArH), 7.62 (t,

³J = 7.2 Hz, 1 H, ArH), 7.89–7.92 (m, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 55.4 (CH₂), 71.4 (CI), 127.2 (ArC), 128.4

(ArC), 128.6 (ArC), 130.5 (ArC), 131.4 (ArC), 131.5 (ArC), 132.9

(ArC), 147.1 (Csp²), 152.6 (Csp²) ppm. HRMS (ESI): m/z calcd.

for C₁₆H₁₁Cl³⁵INO [M + H] 395.9652; found 395.9616.

Yield 0.24 g (68%); yellow solid; m.p. 174–175 °C. IR (KBr): ν

˜

max

= 1747 (C=O), 3242 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

3

3.84 (s, 3 H, OCH₃), 4.23 (d, J = 1.2 Hz, 2 H, CH₂), 6.12 (br. s, 1

3

H, NH), 6.91 (d, J = 8.8 Hz, 2 H, ArH), 7.57 (d, J = 8.8 Hz, 2

H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 51.8 (CH₂), 55.3

(OCH₃), 62.8 (CI), 113.3 (ArC), 125.7 (ArC), 130.6 (ArC), 148.9

(Csp²), 150.8 (NHCO), 160.6 (ArC) ppm. HRMS (ESI): m/z calcd.

for C₁₁H₁₀INNaO₃[M + Na] 353.9598; found 353.9595.

(E)-5-[(4-Chlorophenyl)iodomethylene]-2-phenyl-4,5-dihydrooxazole

(12ga): Yield 0.16 g (41%); white solid; m.p. 141–142 °C. ¹H NMR

(400 MHz, CDCl₃): δ = 4.55 (s, 2 H, CH₂), 7.37–7.43 (m, 4 H,

ArH), 7.62 (t, ³J = 7.2 Hz, 1 H, ArH), 7.89–7.92 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.4 (CH₂), 71.4

(CI), 127.2 (ArC), 128.4 (ArC), 128.6 (ArC), 130.5 (ArC), 131.4

(ArC), 131.5 (ArC), 132.9 (ArC), 147.1 (Csp²), 152.6 (Csp²) ppm.

HRMS (ESI): m/z calcd. for C₁₆H₁₁Cl³⁵INO [M + H] 395.9652;

found 395.9616.

5-Bromo-6-(4-methoxyphenyl)-3,4-dihydro-2H-1,3-oxazin-2-one

(8ab): Yield 0.09 g (30%); yellow solid; m.p. 166–167 °C. IR (KBr):

ν

_max= 1737 (C=O), 3271 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃):

˜

δ = 3.84 (s, 3 H, OCH₃), 4.23 (s, 2 H, CH₂), 6.61 (br. s, 1 H, NH),

6.92 (d, ³J = 8.0 Hz, 2 H, ArH), 7.64 (d, ³J = 8.0 Hz, 2 H,

ArH), ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 47.8 (CH₂), 55.3

(OCH₃), 92.3 (CBr), 113.4 (ArC), 123.8 (ArC), 130.2 (ArC), 146.1

(Csp²), 150.8 (NHCO), 160.6 (ArC) ppm. HRMS (ESI): m/z calcd.

for C₁₁H₁₀⁷⁹BrNNaO₃[M + Na] 305.9736; found 305.9732.

(4-Chlorophenyl)(2-phenyloxazol-5-yl)methanone (21ga): Yield

6-(3,4-Dimethoxyphenyl)-5-iodo-3,4-dihydro-2H-1,3-oxazin-2-one

49 mg (18%); white solid; m.p. 142–143 °C. IR (KBr): ν

= 1654 (8ba): Yield 0.24 g (67 %); brownish solid; m.p. 186–189 °C. IR

˜

max

(C=O) cm^–1. H NMR (400 MHz, CDCl₃): δ = 7.50–7.56 (m, 5 H, (KBr): ν

= 1724 (C=O), 3246 (NH) cm^–1. H NMR (400 MHz,

1

˜

max

ArH), 7.89 (s, 1 H, CH), 7.96–7.98 (m, 2 H, ArH), 8.19 (dd, J = CDCl₃): δ = 3.91 (s, 6 H, 2ϫOCH₃), 4.23 (d, ³J = 1.6 Hz, 2 H,

3

4

3

8.1, J = 1.6 Hz, 1 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ

CH₂), 6.31 (br. s, 1 H, NH), 6.87 (d, J = 8.4 Hz, 1 H, ArH), 7.12

4

3

4

= 126.1 (ArC), 127.5 (ArC), 129.0 (ArC), 129.1 (ArC), 130.4 (ArC), (d, J = 2.0 Hz, 1 H, ArH), 7.24 (dd, J = 8.4, J = 2.0 Hz, 1 H,

7100

www.eurjoc.org

Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

3

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 51.8 (CH₂), 55.9 (d, J = 1.6 Hz, 2 H, CH₂), 6.70 (br. s, 1 H, NH), 7.39–7.42 (m, 3

(OCH₃), 56.0 (OCH₃), 63.0 (CI), 110.2 (ArC), 111.9 (ArC), 122.5 H, ArH), 7.60–7.62 (m, 2 H, ArH), ppm. ¹³C NMR (100 MHz,

(ArC), 125.8 (ArC), 148.3 (ArC), 148.8 (Csp²), 150.2 (ArC), 150.8 CDCl₃): δ = 51.6 (CH₂), 64.1 (CI), 128.0 (ArC), 129.1 (ArC), 130.0

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₂H₁₂INNaO₄[M +

Na] 383.9703; found 383.9708.

(ArC), 133.4 (ArC), 148.9 (Csp²), 151.0 (NHCO), ppm. HRMS

(ESI): m/z calcd. for C₁₀H₈INNaO₂[M + Na] 323.9492; found

323.9497.

5-Bromo-6-(3,4-dimethoxyphenyl)-3,4-dihydro-2H-1,3-oxazin-2-one

(8bb): Yield 0.17 g (53%); yellowish white solid; m.p. 162–163 °C.

(E)-tert-Butyl 2,3-Diiodo-3-phenylallylcarbamate (17ea): Yield

43.6 mg (9%); white solid; m.p. 103–104 °C. IR (KBr): ν_max= 1685

˜

IR (KBr): ν max = 1766 (C=O), 3251 (NH) cm^–1

.

¹H NMR

˜

(400 MHz, CDCl₃): δ = 3.89 (s, 3 H, OCH₃), 3.90 (s, 3 H, OCH₃), (C=O), 3384 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.49 (s,

3

4.22 (d, J = 1.6 Hz, 2 H, CH₂), 6.71 (br. s, 1 H, NH), 6.87 (d, J

9 H, 3ϫCH₃), 4.33 (d, ³J = 2.0 Hz, 2 H, CH₂), 4.97 (br. s, 1 H,

4

3

= 8.4 Hz, 1 H, ArH), 7.18 (d, J = 2.0 Hz, 1 H, ArH), 7.30 (dd, J NH), 7.20 (d, ³J = 7.2 Hz, 2 H, ArH), 7.27–7.31 (m, 1 H, ArH),

4

= 8.4, J = 2.0 Hz, 1 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): 7.36 (t, ³J = 7.2 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃):

δ = 47.8 (CH₂), 55.8 (OCH₃), 55.9 (OCH₃), 92.5 (CBr), 110.3 δ = 28.4 (3ϫCH₃), 57.1 (CH₂), 80.0 [C(CH₃)₃], 96.3 (Csp²I), 102.8

(ArC), 111.4 (ArC), 122.1 (ArC), 123.9 (ArC), 146.0 (ArC), 148.3 (Csp²I), 128.1 (ArC), 128.5 (ArC), 131.7 (ArC), 147.5 (ArC), 155.3

(Csp²), 150.2 (ArC), 150.8 (NHCO) ppm. HRMS (ESI): m/z calcd. (NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₄H₁₇I₂NNaO₂[M +

for C₁₂H₁₂⁷⁹BrNO₄314.0022 [M + H]; found 314.0037.

Na] 507.9241; found 507.9244.

6-(Benzo[d][1,3]dioxol-5-yl)-5-iodo-3,4-dihydro-2H-1,3-oxazin-2-one 5-Bromo-6-phenyl-3,4-dihydro-2H-1,3-oxazin-2-one (8eb): Yield

(8ca): Yield 0.21 g (60%); white solid; m.p. 203–204 °C. IR (KBr):

= 1737 (C=O), 3278 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]-

0.1 g (39%); white solid; m.p. 154–155 °C. IR (KBr): ν

= 1721

max

˜

ν

˜

(C=O), 3380 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 4.24

max

3

DMSO): δ = 4.07 (d, ³J = 1.2 Hz, 2 H, CH₂), 6.09 (s, 2 H, OCH₂O), (d, J = 1.2 Hz, 2 H, CH₂), 7.05 (br. s, 1 H, NH), 7.40–7.42 (m, 3

3

4

6.98 (d, J = 7.6 Hz, 1 H, ArH), 7.03 (d, J = 1.6 Hz, 1 H, ArH),

H, ArH), 7.66–7.69 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

7.05 (br. s, 1 H, ArH), 7.91 (br. s, 1 H, NH) ppm. ¹³C NMR CDCl₃): δ = 47.7 (CH₂), 93.6 (CBr), 128.0 (ArC), 128.6 (ArC),

(100 MHz, [D₆]DMSO): δ = 50.6 (CH₂), 66.3 (CI), 101.6 (OCH₂O), 129.9 (ArC), 131.4 (ArC), 146.1 (Csp²), 151.0 (NHCO) ppm.

108.0 (ArC), 109.1 (ArC), 123.5 (ArC), 127.7 (ArC), 146.9 (ArC),

HRMS (ESI): m/z calcd. for C₁₀H₈⁷⁹BrNNaO₂[M + Na] 275.9631;

147.8 (Csp²), 148.1 (ArC), 149.3 (NHCO) ppm. HRMS (ESI): m/z found 275.9635.

calcd. for C₁₁H₈INNaO₄[M + Na] 367.9390; found 367.9391.

5,5Ј-Dibromo-6,6Ј-diphenyl-3Ј,4Ј-dihydro-2ЈH-3,4Ј-bi(1,3-oxazine)-

5-Iodo-6-p-tolyl-3,4-dihydro-2H-1,3-oxazin-2-one (8da): Yield 0.2 g 2,2Ј(4H)-dione (22eb): Yield 17.6 mg (7%); white solid; m.p. 203–

1

(65 %); yellow solid; m.p. 183–184 °C. IR (KBr): ν

= 1747

204 °C. IR (KBr): ν

= 1717 (C=O), 3288 (NH) cm^–1. H NMR

˜

max

(C=O), 3242 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.83 (s, (400 MHz, [D₆]DMSO): δ = 4.24 (s, 2 H, CH₂), 6.30 (s, 1 H, CH),

3 H, CH₃), 4.22 (d, J = 1.6 Hz, 2 H, CH₂), 6.69 (br. s, 1 H, NH), 7.49–7.52 (m, 6 H, ArH), 7.64–7.69 (m, 4 H, ArH), 9.00 (d, ³J =

3

7.21 (d, ³J = 8.0 Hz, 2 H, ArH), 7.51 (d, ³J = 8.0 Hz, 2 H, 2.4 Hz, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ =

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.4 (CH₃), 51.6 47.4 (CH₂), 68.2 (CH), 93.0 (CBr), 94.3 (CBr), 128.8 (ArC), 128.9

(CH₂), 63.5 (CI), 128.7 (ArC), 128.9 (ArC), 130.5 (ArC), 140.1 (2ϫArC), 129.2 (ArC), 130.6 (ArC), 130.9 (ArC), 131.5 (ArC),

(ArC), 149.0 (Csp²), 151.1 (NHCO) ppm. HRMS (ESI): m/z calcd. 131.8 (ArC), 145.6 (Csp²), 148.5 (2ϫNHCO), 150.3 (Csp²) ppm.

for C₁₁H₁₀INNaO₂[M + Na] 337.9648; found 337.9643.

HRMS (ESI): m/z calcd. for C₂₀H₁₄⁷⁹Br₂N₂NaO₄[M + Na]

526.9213; found 526.9212.

5-Bromo-6-p-tolyl-3,4-dihydro-2H-1,3-oxazin-2-one (8db): Yield

0.1 g (39%); white solid; m.p. 160–161 °C. IR (KBr): ν

= 1754 6-(4-Chlorophenyl)-5-iodo-3,4-dihydro-2H-1,3-oxazin-2-one (8fa):

˜

max

(C=O), 3248 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.38 (s, Yield 0.17 g (54%); yellow solid; m.p. 209–210 °C. IR (KBr): ν

˜

max

3

3 H, CH₃), 4.23 (d, J = 1.6 Hz, 2 H, CH₂), 6.78 (br. s, 1 H, NH), = 1749 (C=O), 3141 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]DMSO):

7.21 (d, ³J = 8.0 Hz, 2 H, ArH), 7.58 (d, ³J = 8.0 Hz, 2 H, δ = 4.10 (d, ³J = 1.6 Hz, 2 H, CH₂), 7.53 (d, ³J = 8.4 Hz, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.4 (CH₃), 47.8 ArH), 7.58 (d, J = 8.4 Hz, 2 H, ArH), 7.95 (br. s, 1 H, NH) ppm.

3

(CH₂), 93.0 (CBr), 128.5 (ArC), 128.6 (ArC), 128.7 (ArC), 140.1

¹³C NMR (100 MHz, [D₆]DMSO): δ = 50.6 (CH₂), 67.4 (CI), 128.3

(ArC), 146.3 (Csp²), 150.9 (NHCO) ppm. HRMS (ESI): m/z calcd. (ArC), 130.8 (ArC), 132.9 (ArC), 134.2 (ArC), 147.0 (Csp²), 149.0

for C₁₁H₁₀⁷⁹BrNNaO₂[M + Na] 289.9787; found 289.9787.

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₁H₁₀³⁵ClINNaO₂[M

+ Na] 372.9343; found 372.9340.

5,5Ј-Dibromo-6,6Ј-di-p-tolyl-3Ј,4Ј-dihydro-2ЈH-3,4Ј-bi(1,3-oxazine)-

2,2Ј(4H)-dione (22db): Yield 18.6 mg (7%); white solid; m.p. 198–

5-Bromo-6-(4-chlorophenyl)-3,4-dihydro-2H-1,3-oxazin-2-one (8fb):

1

199 °C. IR (KBr): ν

= 1734 (C=O), 3234 (NH) cm^–1. H NMR Yield 0.07 g (24%); white solid; m.p. 203–204 °C. IR (KBr): ν

˜

max

(400 MHz, CDCl₃): δ = 2.38 (s, 3 H, CH₃), 2.41 (s, 3 H, CH₃), 4.07

= 1758 (C=O), 3238 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]DMSO):

2

(d, J = 14.4 Hz, 1 H, CHH), 4.19 (d, J = 14.4 Hz, 1 H, CHH),

δ = 4.14 (d, ³J = 1.6 Hz, 2 H, CH₂), 7.55 (d, ³J = 8.8 Hz, 2 H,

6.55 (d, ³J = 3.2 Hz, 1 H, CH), 6.65 (d, ³J = 2.8 Hz, 1 H, NH), ArH), 7.63 (d, J = 8.4 Hz, 2 H, ArH), 8.14 (br. s, 1 H, NH) ppm.

3

7.21 (d, J = 8.0 Hz, 2 H, ArH), 7.26 (d, J = 8.0 Hz, 2 H, ArH),

¹³C NMR (100 MHz, [D₆]DMSO): δ = 46.8 (CH₂), 95.2 (CBr),

7.59 (d, ³J = 8.4 Hz, 2 H, ArH), 7.59 (d, ³J = 8.0 Hz, 2 H, 128.5 (ArC), 130.3 (ArC), 130.7 (ArC), 134.4 (ArC), 144.6

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.4 (CH₃), 21.5 (Csp²), 148.7 (NHCO) ppm. HRMS (ESI): m/z calcd. for

(CH₃), 45.7 (CH₂), 67.8 (CH), 90.5 (CBr), 92.2 (CBr), 127.6 (ArC), C₁₀H₇⁷⁹Br³⁵ClNNaO₂[M + Na] 309.9241; found 309.9241.

127.8 (ArC), 128.4 (ArC), 128.6 (ArC), 128.8 (ArC), 129.0 (ArC),

5,5Ј-Dibromo-6,6Ј-bis(4-chlorophenyl)-3Ј,4Ј-dihydro-2ЈH-3,4Ј-bi-

140.4 (ArC), 141.3 (ArC), 146.0 (Csp²), 148.5 (NHCO), 149.8

(1,3-oxazine)-2,2Ј(4H)-dione (22fb): Yield 40 mg (14%); white solid;

(NHCO), 151.3 (Csp²) ppm. HRMS (ESI): m/z calcd. for

m.p. 123–124 °C. IR (KBr): ν

= 1734 (C=O), 3175 (NH) cm^–1.

˜

max

C₂₂H₁₈⁷⁹Br₂N₂NaO₄[M + Na] 554.9526; found 554.9523.

¹H NMR (400 MHz, [D₆]DMSO): δ = 4.22 (d, J = 15.6 Hz, 1 H,

2

5-Iodo-6-phenyl-3,4-dihydro-2H-1,3-oxazin-2-one (8ea): Yield 0.16 g CHH), 4.27 (d, J = 15.2 Hz, 1 H, CHH), 6.28 (s, 1 H, CH), 7.57

3

(52 %); yellow solid; m.p. 165–166 °C. IR (KBr): ν

= 1723

(d, J = 3.2 Hz, 2 H, ArH), 7.59 (d, J = 3.6 Hz, 2 H, ArH), 7.68

˜

max

3

(C=O), 3386 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 4.24

(d, J = 8.8 Hz, 2 H, ArH), 7.71 (d, J = 8.4 Hz, 2 H, ArH), 7.59

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7101

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

(d, ³J = 2.4 Hz, 2 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO):

δ = 47.1 (CH₂), 67.7 (CH), 93.0 (CBr), 94.6 (CBr), 128.5 (ArC),

7.57 (d, ³J = 7.9 Hz, 2 H, ArH), 9.15 (s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, [D₆]DMSO): δ = 21.3 (CH₃), 21.4 (CH₃), 49.5 (CH₂),

128.6 (ArC), 129.8 (ArC), 130.2 (ArC), 130.3 (ArC), 130.7 (ArC), 68.6 (CI), 126.6 (ArC), 129.1 (ArC), 129.3 (ArC), 129.5 (ArC),

134.8 (ArC), 135.0 (ArC), 144.1 (Csp²), 147.8 (NHCO), 147.9 129.7 (ArC), 140.4 (ArC), 140. 9 (ArC), 142.3 (ArC), 146.3 (C-sp²),

(NHCO), 148.8 (Csp²) ppm. HRMS (ESI): m/z calcd. for 152.9 (HNC-sp²) ppm. HRMS (ESI): m/z calcd. for C₁₈H₁₈IN₂O₃S

C₂₀H₁₂⁷⁹Br₂³⁵Cl₂KN₂O₄[M + K] 610.8172; found 610.8162.

[M + H] 469.0077; found 469.0072.

(E)-5-[Iodo(4-nitrophenyl)methylene]oxazolidin-2-one (13ga): Yield

N-(5-Iodo-6-phenyl-4H-1,3-oxazin-2-yl)-4-methylbenzenesulfon-

58.8 mg (17%); yellow solid; m.p. 203–204 °C. IR (KBr): ν

=

amide (9ga): Yield 0.27 g (59%); white solid; m.p. 204–208 °C. IR

˜

max

1812 (C=O), 3302 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = (KBr): ν

= 3284 (NH) cm^–1. H NMR (400 MHz, [D₆]DMSO):

1

˜

max

3

4.34 (s, 2 H, CH₂), 7.77 (d, J = 9.2 Hz, 2 H, ArH), 8.23 (d, J =

9.2 Hz, 2 H, ArH), 8.74 (br. s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 50.2 (CH₂), 68.7 (CI), 123.5 (ArC), 130.5

δ = 2.33 (s, 3 H, CH₃), 4.17 (s, 2 H, CH₂), 7.21 (d, J = 7.3 Hz, 2

H, ArH), 7.46 (br. s, 5 H, ArH), 7.58 (d, J = 7.5 Hz, 2 H, ArH),

3

9.17 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ =

(ArC), 144.1 (ArC), 146.1 (ArC), 149.7 (Csp²), 155.6 21.4 (CH₃), 49.5 (CH₂), 69.2 (IC-sp²), 126.6 (ArC), 128.6 (ArC),

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₀H₇IN₂NaO₄[M +

Na] 368.9343; found 368.9348.

129.4 (ArC), 129.5 (ArC), 130.6 (ArC), 132.6 (ArC), 140.9 (ArC),

142.3 (ArC), 146.2 (ICC-sp²), 152.8 (HNC-sp²) ppm. HRMS

(ESI): m/z calcd. for C₁₇H₁₅IN₂NaO₃S [M + Na] 476.9740; found

476.9731.

(E)-5-[Bromo(4-nitrophenyl)methylene]oxazolidin-2-one (13gb):

Yield 32.7 mg (11%); yellow oil. IR (KBr): ν

= 1735 (C=O),

˜

max

3302 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 4.48 (s, 2 H, (E)-N-[5-(Iodomethylene)-4,5-dihydrooxazol-2-yl]-4-methylbenzene-

3

CH₂), 6.18 (br. s, 1 H, NH), 7.90 (d, J = 8.8 Hz, 2 H, ArH), 8.22 sulfonamide (14ia): Yield 0.27 g (71 %); white solid; m.p. 218–

3

(d, J = 8.8 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ

223 °C. IR (KBr): ν

= 3364 (NH) cm^–1. ¹H NMR (400 MHz,

˜

max

= 47.6 (CH₂), 93.4 (CBr), 123.5 (ArC), 129.4 (ArC), 140.1 (ArC), [D₆]DMSO): δ = 2.36 (s, 3 H, CH₃), 4.27 (s, 2 H, CH₂), 6.22 (s, 1

145.6 (ArC), 147.0 (Csp²), 155.6 (NHCO) ppm. HRMS (ESI): m/z H, ICH), 7.35 (br. s, 2 H, ArH), 7.73 (br. s, 2 H, ArH), 9.40 (br. s,

calcd. for C₁₀H₇⁷⁹BrN₂NaO₄[M + Na] 320.9481; found 320.9482. 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.4 (CH₃),

46.3 (CH₂), 54.1 (IC-sp²), 126.6 (ArC), 129.8 (ArC), 140.0 (ArC),

(E)-tert-Butyl 2,3-Diiodoallylcarbamate (17ha): Yield 0.11 g (26%);

142.9 (ArC), 151.1 (ICC-sp²), 159.2 (HNC-sp²) ppm. HRMS (ESI):

white solid; m.p. 72–73 °C. IR (KBr): ν

= 1699 (C=O), 3379

˜

max

m/z calcd. for C₁₁H₁₂IN₂O₃S [M + H] 378.9608; found 378.9611.

(NH) cm^–1

.

¹H NMR (400 MHz, CDCl₃): δ = 1.46 (s, 9 H,

3

3ϫCH₃), 4.00 (d, J = 5.6 Hz, 2 H, CH₂), 4.88 (br. s, 1 H, NH),

7.02 (s, 1 H, Csp²H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.4

(3 ϫ CH₃), 51.8 (CH₂), 80.0 [C(CH₃)₃], 80.4 (Csp²HI), 102.0

(E)-N-(2,3-Diiodoallylcarbamoyl)-4-methylbenzenesulfonamide

(18ia): Yield 80.9 mg (16 %); white solid; m.p. 184–187 °C. IR

(KBr): ν

= 3234 (NH), 1691 (CO) cm^–1. ¹H NMR (400 MHz,

˜

max

(Csp²I), 155.2 (NHCO) ppm. HRMS (ESI): m/z calcd. for [D₆]DMSO): δ = 2.34 (s, 3 H, CH₃), 3.80 (d, ³J = 5.5 Hz, 2 H,

3

C₈H₁₃I₂NNaO₂[M + Na] 431.8928; found 431.8926.

CH₂), 6.86 (t, J = 5.8 Hz, 1 H, NH), 7.30 (s, 1 H, CH), 7.41 (d,

³J = 8.1 Hz, 2 H, ArH), 7.80 (d, ³J = 8.3 Hz, 2 H, ArH), 10.76

(br. s, 1 H, NH) ppm. HRMS (ESI): m/z calcd. for C₁₁H₁₂I₂N_2-

NaO₃S [M + Na] 528.8550; found 528.8555.

N-[5-Iodo-6-(4-methoxyphenyl)-4H-1,3-oxazin-2-yl]-4-methylbenz-

enesulfonamide (9aa): Yield 0.35 g (73%); white solid; m.p. 190–

195 °C (decomp.). IR (KBr): ν

= 3278 (NH) cm^–1. ¹H NMR

˜

max

(400 MHz, CDCl₃): δ = 2.39 (s, 3 H, CH₃), 3.88 (s, 3 H, OCH₃),

(E)-5-(Iodomethylene)-N-phenyl-4,5-dihydrooxazol-2-amine (14ja):

3

4.33 (s, 2 H, NCH₂), 6.93 (d, J = 8.8 Hz, 2 H, ArH), 7.17 (d, J Yield 0.15 g (47%); white solid; m.p. 152–155 °C. IR (KBr): ν

˜

max

3

1

= 8.1 Hz, 2 H, ArH), 7.52 (d, J = 8.8 Hz, 2 H, ArH), 7.71 (d, J

= 3233(NH) cm^–1. H NMR (400 MHz, [D₆]DMSO): δ = 4.38 (d,

= 8.2 Hz, 2 H, ArH), 9.13 (br. s, 1 H, HN) ppm. ¹³C NMR ⁴J = 2.5 Hz, 2 H, CH₂), 5.88 (s, 1 H, CH), 6.95 (t, J = 7.3 Hz, 1

3

(100 MHz, CDCl₃): δ = 21.5 (CH₃), 49.8 (NCH₂), 55.4 (OCH₃), H, ArH), 7.26 (t, J = 7.9 Hz, 2 H, ArH), 7.55 (d, J = 7.1 Hz, 2

64.8 (CI), 113.4 (ArC), 124.2 (ArC), 126.9 (ArC), 129.2 (ArC), H, ArH), 9.65 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]-

130.9 (ArC), 139.2 (ArC), 142.8 (ArC), 147.2 (C-sp²), 153.8

(HNC-sp²), 160.9 (ArC) ppm. HRMS (ESI): m/z calcd. for

C₁₈H₁₇IN₂NaO₄S [M + Na] 506.9846; found 506.9842.

DMSO): δ = 48.3 (IC-sp²), 59.3 (CH₂), 118.2 (ArC), 122.2 (ArC),

129.2 (ArC), 139.9 (ArC), 155.3 (H₂CC-sp²), 156.5 (HNC-

sp²) ppm. HRMS (ESI): m/z calcd. for C₁₀H₁₀IN₂O [M + H]

300.9832; found 300.9830.

N-[6-(3,4-Dimethoxyphenyl)-5-iodo-4H-1,3-oxazin-2-yl]-4-methyl-

benzenesulfonamide (9da): Yield 0.28 g (55%); off-white powder; (E)-N-Benzyl-5-(iodomethylene)-4,5-dihydrooxazol-2-amine (14ka):

m.p. 211 °C. IR (KBr): ν

= 3003 (NH) cm^–1

.

¹H NMR Yield 0.14 g (49%); white solid; m.p 103–105 °C. IR (KBr): ν

=

˜

max

(400 MHz, [D₆]DMSO): δ = 2.32 (s, 3 H, CH₃), 3.79 (s, 3 H, 3442(NH) cm^–1. H NMR (400 MHz, [D₆]DMSO): δ = 4.17 (d, J

1

4

OCH₃), 3.83 (s, 3 H, OCH₃), 4.15 (s, 2 H, CH₂), 7.04 (d, ³J = = 2.4 Hz, 2 H, CH₂), 4.27 (s, 2 H, CH₂), 5.77 (s, 1 H, CH), 7.20–

3

8.3 Hz, 1 H, ArH), 7.17 (d, J = 8.2 Hz, 1 H, ArH), 7.20–7.34 (m, 7.40 (m, 5 H, ArH), 7.48 (br. s, 1 H, NH) ppm. ¹³C NMR

3 H, ArH), 7.60 (d, ³J = 7.6 Hz, 2 H, ArH), 9.19 (br. s, 1 H,

(100 MHz, [D₆]DMSO): δ = 45.7 (NCH₂), 47.7 (IC-sp²), 58.7

NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.3 (CH₃), 49.6 (HNCH₂), 127.3 (ArC), 127.6 (ArC), 128.7 (ArC), 139.8 (ArC),

(CH₂), 56.0 (2ϫOCH₃), 67.6 (IC-sp²), 111.4 (ArC), 112.8 (ArC), 158.4 (H₂CC-sp²), 159.7 (HNC-sp²) ppm. HRMS (ESI): m/z calcd.

122.9 (ArC), 124.6 (ArC), 126.6 (ArC), 129.5 (ArC), 140.1 (ArC), for C₁₁H₁₂IN₂NaO [M + H] 337.9892; found 337.9894.

142.3 (ArC), 146.2 (ArC), 148.4 (ICC-sp²), 150.5 (ArC), 153.1

N-[5-Iodo-6-(4-methoxyphenyl)-4H-1,3-thiazin-2-yl]benzamide

(HNC-sp²) ppm. HRMS (ESI): m/z calcd. for C₁₉H₁₉IN₂NaO₅S

(10aa): Yield 0.27 g (59 %); yellow solid; m.p. 149–150 °C. IR

[M + Na] 536.9952; found 536.9950.

1

(KBr): ν

= 1680 (C=O), 3238 (NH) cm^–1. H NMR (400 MHz,

˜

max

3

N-[5-Iodo-6-(p-tolyl)-4H-1,3-oxazin-2-yl]-4-methylbenzenesulfon-

amide (9fa): Yield 0.44 g (93%); yellowish solid; m.p. 234 °C (de-

CDCl₃): δ = 3.83 (s, 3 H, OCH₃), 4.52 (s, 2 H, CH₂), 6.92 (d, J =

8.8 Hz, 2 H, ArH), 7.35 (d, J = 8.8 Hz, 2 H, ArH), 7.43 (t, J =

3

4

comp.). IR (KBr): ν

= 3000 (NH) cm^–1. ¹H NMR (400 MHz, 7.6 Hz, 2 H, ArH), 7.52 (tt, J = 7.6, J = 1.2 Hz, 1 H, ArH), 8.08

˜

max

3

[D₆]DMSO): δ = 2.33 (s, 3 H, CH₃), 2.36 (s, 3 H, CH₃), 4.14 (br. s,

(d, J = 7.2 Hz, 2 H, ArH), 10.61 (br. s, 1 H, NH) ppm. ¹³C NMR

2 H, CH₂), 7.20–7.28 (m, 4 H, ArH), 7.30–7.38 (m, 2 H, ArH), (100 MHz, CDCl₃): δ = 55.3 (OCH₃), 57.7 (CH₂), 78.1 (CI), 113.9

7102

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Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

(ArC), 128.3 (ArC), 128.9 (ArC), 130.5 (ArC), 130.8 (ArC), 132.4

δ = 4.30 (d, ⁴J = 2.8 Hz, 2 H, CH₂), 6.57 (t, ⁴J = 2.8 Hz, 1 H, CH),

3

4

(ArC), 135.0 (ArC), 135.1 (Csp²), 160.3 (ArC), 164.1 (Csp²), 174.0 7.48 (t, J = 7.2 Hz, 2 H, ArH), 7.57 (tt, J = 7.2, J = 1.2 Hz, 1

(CO) ppm. HRMS (ESI): m/z calcd. for C₁₈H₁₆IN₂O₂S [M + H]

450.9972; found 450.9980.

H, ArH), 8.05–8.08 (m, 2 H, ArH), 10.54 (br. s, 1 H, NH) ppm.

¹³C NMR (100 MHz, [D₆]DMSO): δ = 56.6 (CH₂), 65.9 (CH),

128.3 (ArC), 128.7 (ArC), 132.3 (ArC), 134.8 (Csp²), 143.3 (ArC),

167.4 (Csp²), 172.0 (CO) ppm. HRMS (ESI): m/z calcd. for

C₁₁H₉IN₂OS [M + H] 344.9553; found 344.9544.

N-(5-Iodo-6-phenyl-4H-1,3-thiazin-2-yl)benzamide (10ca): Yield

0.08 g (18%); white solid; m.p. 172–173 °C. IR (KBr): ν

= 1608

˜

max

(C=O), 3406 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]DMSO): δ =

2-Iodo-1-(4-methoxyphenyl)prop-2-en-1-one (11aa): Yield 0.17 g

4.57 (s, 2 H, CH₂), 7.33–7.36 (m, 2 H, ArH), 7.42–7.50 (m, 5 H,

(60%); yellowish oil. IR (KBr): ν_max= 1653 (C=O) cm^–1. ¹H NMR

3

˜

ArH), 7.58 (t, J = 7.6 Hz, 1 H, ArH), 8.00 (d, J = 7.6 Hz, 2 H,

ArH), 10.95 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]

DMSO): δ = 57.3 (CH₂), 82.9 (CI), 128.3 (ArC), 128.5 (ArC), 128.8

(ArC), 129.0 (ArC), 129.1 (ArC), 132.3 (ArC), 134.6 (Csp²), 138.9

(ArC), 140.3 (ArC), 165.4 (Csp²), 174.1 (CO) ppm. HRMS (ESI):

m/z calcd. for C₁₇H₁₃IN₂OS [M + H] 420.9866; found 420.9873.

2

(400 MHz, CDCl₃): δ = 3.91 (s, 3 H, OCH₃), 6.70 (d, J_H,H

=

2

2.4 Hz, 1 H, =CH), 6.77 (d, J_H,H= 2.4 Hz, 1 H, =CH), 6.93 (d,

³J_H,H= 9.2 Hz, 2 H, ArH), 7.90 (d, J_H,H= 9.2 Hz, 2 H,

3

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.57 (OCH₃),

106.76 (=C-I), 113.91 (ArC), 126.15 (=CH₂), 132.57 (ArC), 135.82

(ArC), 163.91 (ArC), 190.63 (C=O) ppm. HRMS (ES): m/z calcd.

for C₁₀H₉INaO₂[M + Na]⁺310.9539; found 310.9537.

(E)-N-{5-[Iodo(phenyl)methylene]-4,5-dihydrothiazol-2-yl}benzamide

(15ca): Yield 0.11 g (25 %); yellow solid; m.p. 195–196 °C. IR

1

(KBr): ν

= 1693 (C=O), 3138 (NH) cm^–1. H NMR (400 MHz,

(E)-2,3-Diiodo-3-(4-methoxyphenyl)allyl Acetate (20aa): Yield

˜

max

0.12 g (27%); yellowish wax. IR (KBr): ν_max= 1726 (CO) cm^–1. ¹H

˜

[D₆]DMSO): δ = 4.50 (s, 2 H, CH₂), 7.33–7.37 (m, 1 H, ArH),

7.42–7.49 (m, 6 H, ArH), 7.56 (t, ³J = 7.2 Hz, 1 H, ArH), 8.01–

8.03 (m, 2 H, ArH), 10.64 (br. s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, [D₆]DMSO): δ = 57.3 (CH₂), 82.5 (CI), 128.2 (ArC),

128.3 (ArC), 128.7 (2 ϫ ArC), 128.8 (ArC), 132.3 (ArC), 134.6

(Csp²), 139.8 (ArC), 142.6 (ArC), 163.3 (Csp²), 172.2 (CO) ppm.

HRMS (ESI): m/z calcd. for C₁₇H₁₃IN₂OS [M + H] 420.9866;

found 420.9876.

NMR (400 MHz, CDCl₃): δ = 2.17 (s, 3 H, CH₃), 3.82 (s, 3 H,

OCH₃), 5.06 (s, 2 H, OCH₂), 6.87 (d, ³J = 8.8 Hz, 1 H, ArH), 7.19

3

(d, J = 8.3 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ

= 20.9 (CH₃), 55.3 (OCH₃), 76.5 (OCH₂), 96.7 (Csp₂-I), 99.6 (Csp₂-

I), 113.7 (ArC), 129.6 (ArC), 139.7 (ArC), 159.5 (ArC), 170.1

(C=O) ppm. HRMS (ESI): m/z calcd. for C₁₂H₁₃I₂O₃[M + H]

458.8954; found 458.8966.

General Procedures for the Phenyl Hypochloroselenoite Mediated

Reactions

(E)-N-{5-[Bromo(4-methoxyphenyl)methylene]-4,5-dihydrothiazol-2-

yl}benzamide (15ab): Yield 0.27 g (68%); yellow solid; m.p. 195–

1

196 °C. IR (KBr): ν

= 1687 (C=O), 3127 (NH) cm^–1. H NMR

˜

max

Method A: To a solution of the corresponding N-(3-substituted

prop-2-ynyl)benzamide 1 (0.5 mmol) in anhydrous dichlorometh-

ane (5 mL), phenyl hypochloroselenoite (95.96 mg, 0.5 mmol) to-

gether with potassium tert-butanoate (0.5 mmol) were added. The

reaction mixture was stirred at room temperature.

(400 MHz, CDCl₃): δ = 3.83 (s, 3 H, OCH₃), 4.44 (s, 2 H, CH₂),

6.89 (d, ³J = 8.8 Hz, 2 H, ArH), 7.45–7.49 (m, 4 H, ArH), 7.57 (tt,

4

³J = 7.6, J = 1.2 Hz, 1 H, ArH), 7.91–7.93 (m, 2 H, ArH), 10.03

(br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 55.3

(OCH₃), 61.3 (CH₂), 108.3 (Csp²), 114.0 (ArC), 128.4 (ArC), 129.0

(ArC), 129.7 (ArC), 131.5 (ArC), 132.8 (ArC), 133.4 (ArC), 134.7

(Csp²), 159.9 (ArC), 163.8 (Csp²), 169.9 (CO) ppm. HRMS (ESI):

m/z calcd. for C₁₈H₁₆⁷⁹BrN₂O₂S [M + H] 403.0110; found

403.0106.

Method B: To a solution of the corresponding tert-butyl prop-2-

ynylcarbamate 2 (0.5 mmol) in anhydrous acetonitrile (5 mL),

phenyl hypochloroselenoite (95.96 mg, 0.5 mmol) together with

potassium phosphate monohydrate (0.5 mmol) were added. The re-

action mixture was stirred at room temperature.

(E)-N-{5-[Bromo(4-chlorophenyl)methylene]-4,5-dihydrothiazol-2-

Method C: To a cooled solution of urea 3 (0.5 mmol) in anhydrous

acetonitrile (5 mL) or to a cooled solution of thiourea 4 (0.5 mmol)

in anhydrous dichloromethane, phenyl hypochloroselenoite

(95.96 mg, 0.5 mmol) was added at 0 °C. The resulting mixtures

were warmed and stirred at room temperature.

yl}benzamide (15bb): Yield 0.18 g (44%); yellow solid; m.p. 234–

1

235 °C. IR (KBr): ν

= 1628 (C=O), 3419 (NH) cm^–1. H NMR

˜

max

(400 MHz, [D₆]DMSO): δ = 4.62 (s, 2 H, CH₂), 7.48 (t, ³J = 7.6 Hz,

2 H, ArH), 7.55–7.60 (m, 5 H, ArH), 8.02–8.05 (m, 2 H, ArH),

10.81 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ

= 59.7 (CH₂), 105.0 (Csp²), 128.4 (ArC), 128.6 (ArC), 128.9 (ArC),

130.0 (ArC), 130.6 (ArC), 132.5 (ArC), 133.5 (ArC), 134.3 (Csp²),

137.7 (ArC), 161.2 (Csp²), 169.1 (CO) ppm. HRMS (ESI): m/z

calcd. for C₁₇H₁₂⁷⁹Br³⁵ClN₂OS [M + H] 405.9542; found 405.9543.

Isolation Procedures for All Products: When completion of the reac-

tion was observed by TLC, the solution was evaporated under re-

duced pressure and the residue was purified by flash column

chromatography eluting with hexane/ethyl acetate mixtures.

(E)-N-{5-[Bromo(phenyl)methylene]-4,5-dihydrothiazol-2-yl}-

6-(4-Methoxyphenyl)-2-phenyl-5-(phenylselanyl)-4H-1,3-oxazine

1

benzamide (15cb): Yield 0.25 g (67 %); yellow solid; m.p. 190–

(7ab): Yield 0.14 g (66%); yellowish oil. H NMR (400 MHz, [D₆]-

1

= 1688 (C=O), 3138 (NH) cm^–1. H NMR

3

191 °C. IR (KBr): ν

˜

DMSO): δ = 2.87 (s, 3 H, OCH₃), 3.29 (s, 2 H, CH₂), 6.10 (d, J

max

3

(400 MHz, [D₆]DMSO): δ = 4.61 (s, 2 H, CH₂), 7.40 (tt, J = 7.2,

⁴J = 1.2 Hz, 1 H, ArH), 7.45–7.54 (m, 6 H, ArH), 7.57 (t, ³J =

7.2 Hz, 1 H, ArH), 8.03–8.05 (m, 2 H, ArH), 10.87 (br. s, 1 H,

NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 54.9 (CH₂),

106.7 (CBr), 128.1 (ArC), 128.3 (ArC), 128.7 (ArC), 128.8 (ArC),

129.1 (ArC), 132.4 (ArC), 134.4 (Csp²), 137.1 (ArC), 138.8 (ArC),

167.9 (Csp²), 174.2 (CO) ppm. HRMS (ESI): m/z calcd. for

C₁₇H₁₃⁷⁹BrN₂OS [M + H] 371.9932; found 371.9935.

= 8.8 Hz, 2 H, ArH), 6.34–6.43 (m, 3 H, ArH), 6.51–6.57 (m, 4 H,

3

ArH), 6.62 (t, J = 7.6 Hz, 2 H, ArH), 6.68 (d, J = 8.8 Hz, 2 H,

ArH), 6.98–7.00 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, [D₆]-

DMSO): δ = 49.2 (CH₂), 55.3 (OCH₃), 98.7 (Csp²), 113.6 (ArC),

125.3 (ArC), 126.9 (ArC), 127.3 (ArC), 128.4 (ArC), 128.6 (ArC),

129.7 (ArC), 130.1 (ArC), 130.8 (ArC), 131.1 (ArC), 131.4 (ArC),

150.2 (Csp²), 151.8 (Csp²), 160.2 (ArC) ppm. HRMS (ESI): m/z

calcd. for C₂₃H₂₀NO₂Se [M + H] 422.0655; found 422.0647.

(E)-N-[5-(Iodomethylene)-4,5-dihydrothiazol-2-yl]benzamide (15da):

(E)-N-[3-Chloro-3-(4-methoxyphenyl)-2-(phenylselanyl)allyl]benz-

amide (16ab): Yield 29.7 mg (13 %); yellowish oil. ¹H NMR

(400 MHz, CDCl₃): δ = 3.82 (s, 3 H, OCH₃), 4.56 (d, J = 5.6 Hz,

Yield 0. 07 g (20%); white solid; m.p. 195–196 °C. IR (KBr): ν

˜

max

= 1631 (C=O), 3421 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]DMSO):

3

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7103

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

2 H, CH₂), 6.34 (br. s, NH), 6.89 (d, ³J = 8.8 Hz, 2 H, ArH), 7.24– 2-Phenyl-5-(phenylselanyl)-6-(3,4,5-trimethoxyphenyl)-4H-1,3-ox-

7.26 (m, 3 H, ArH), 7.37 (d, ³J = 8.8 Hz, 2 H, ArH), 7.40–7.43 (m,

4 H, ArH), 7.49 (t, ³J = 7.2 Hz, 2 H, ArH), 7.64–7.66 (m, 2 H,

azine (7db): Yield 0.15 g (63%); yellowish oil. ¹H NMR (400 MHz,

CDCl₃): δ = 3.84 (s, 6 H, 2ϫOCH₃), 3.90 (s, 3 H, OCH₃), 4.30 (s,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 43.8 (CH₂), 55.4 2 H, CH₂), 6.89 (s, 2 H, ArH), 7.26–7.29 (m, 3 H, ArH), 7.41 (t,

(OCH₃), 113.5 (ArC), 125.9 (Csp²), 127.0 (ArC), 128.1 (ArC), ³J = 7.6 Hz, 2 H, ArH), 7.45–7.50 (m, 3 H, ArH), 7.96–7.99 (m, 2

128.6 (ArC), 129.4 (ArC), 129.6 (ArC), 130.6 (ArC), 131.52 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 50.0 (CH₂), 56.2

(ArC), 131.59 (ArC), 133.0 (ArC), 134.4 (ArC), 135.2 (Csp²), 160.2 (2ϫOCH₃), 61.0 (OCH₃), 100.6 (Csp²), 106.1 (ArC), 127.2 (ArC),

(ArC), 166.9 (NHCO) ppm. HRMS (ESI): m/z calcd. for 127.5 (ArC), 128.4 (ArC), 128.6 (ArC), 128.8 (ArC), 129.5 (ArC),

C₂₃H₂₀ClNNaO₂Se [M + Na] 480.0238; found 480.0230.

131.2 (ArC), 131.7 (ArC), 132.0 (ArC), 139.1 (ArC), 149.4 (Csp²),

152.81 (Csp²), 152.85 (ArC) ppm. HRMS (ESI): m/z calcd. for

C₂₅H₂₃NNaO₄Se [M + Na] 504.0686; found 504.0687.

6-(4-Ethoxyphenyl)-2-phenyl-5-(phenylselanyl)-4H-1,3-oxazine

(7bb): Yield 0.14 g (65 %); yellowish oil. ¹H NMR (400 MHz,

2,6-Diphenyl-5-(phenylselanyl)-4H-1,3-oxazine (7fb): Yield 0.11 g

3

CDCl₃): δ = 1.44 (t, J = 6.8 Hz, 3 H, OCH₂CH₃), 4.08 (q, J =

1

(57%); yellowish oil. H NMR (400 MHz, CDCl₃): δ = 4.32 (s, 2

3

6.8 Hz, 2 H, OCH₂CH₃), 4.30 (s, 2 H, CH₂), 6.94 (d, J = 9.2 Hz,

H, CH₂), 7.27–7.30 (m, 3 H, ArH), 7.39–7.50 (m, 8 H, ArH), 7.66–

7.69 (m, 2 H, ArH), 7.97–8.00 (m, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 49.8 (CH₂), 101.0 (Csp²), 127.3 (ArC),

127.5 (ArC), 128.1 (ArC), 128.3 (ArC), 128.4 (ArC), 129.8 (ArC),

129.5 (ArC), 129.6 (ArC), 131.2 (ArC), 131.8 (ArC), 132.1 (ArC),

133.6 (ArC), 149.8 (Csp²), 152.8 (Csp²) ppm. HRMS (ESI): m/z

calcd. for C₂₂H₁₇NNaOSe [M + Na] 414.0373; found 414.0380.

2 H, ArH), 7.26–7.28 (m, 3 H, ArH), 7.41 (t, ³J = 7.6 Hz, 2 H,

3

ArH), 7.45–7.49 (m, 3 H, ArH), 7.62 (d, J = 8.8 Hz, 2 H, ArH),

7.97–7.99 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

14.9 (OCH₂CH₃), 50.0 (CH₂), 63.6 (OCH₂CH₃), 99.5 (Csp²), 113.9

(ArC), 125.9 (ArC), 127.33 (ArC), 127.36 (ArC), 128.3 (ArC),

128.7 (ArC), 129.4 (ArC), 130.2 (ArC), 131.1 (ArC), 131.90 (ArC),

131.96 (ArC), 150.0 (Csp²), 152.9 (Csp²), 159.9 (ArC) ppm. HRMS

(ESI): m/z calcd. for C₂₄H₂₂NO₂Se [M + H] 436.0811; found

436.0802.

(E)-2-Phenyl-5-(phenylselanylmethylene)-4,5-dihydrooxazole (12ib):

1

Yield 40.9 mg (26%); yellowish oil. H NMR (400 MHz, CDCl₃):

3

δ = 4.09 (d, J = 0.8 Hz, 2 H, CH₂), 6.78 (s, 1 H, CH), 7.26–7.31

(E)-N-[3-Chloro-3-(4-ethoxyphenyl)-2-(phenylselanyl)allyl]benz-

amide (16bb): Yield 28.3 mg (12 %); yellowish oil. ¹H NMR

(400 MHz, CDCl₃): δ = 1.42 (t, ³J = 6.8 Hz, 3 H, OCH₂CH₃), 4.05

(m, 3 H, ArH), 7.28–7.45 (m, 3 H, ArH), 7.52–7.54 (m, 2 H, ArH),

7.94–7.96 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

20.6 (CH₂), 125.4 (ArC), 126.3 (ArC), 127.4 (ArC), 128.2 (ArC),

128.8 (ArC), 129.2 (ArC), 129.3 (ArC), 130.3 (sp²), 134.6 (ArC),

149.5 (Csp²), 161.4 (Csp²) ppm. HRMS (ESI): m/z calcd. for

C₁₆H₁₃NNaOSe [M + Na] 338.0055; found 338.0061.

3

(q, J = 6.8 Hz, 2 H, OCH₂CH₃), 4.55 (d, J = 5.6 Hz, 2 H, CH₂),

3

6.33 (br. s, NH), 6.87 (d, J = 8.8 Hz, 2 H, ArH), 7.14–7.26 (m, 3

H, ArH), 7.36 (d, ³J = 8.8 Hz, 2 H, ArH), 7.38–7.43 (m, 4 H, ArH),

7.49 (tt, ³J = 7.2, ⁴J = 2.0 Hz, 2 H, ArH), 7.63–7.66 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 14.9 (OCH₂CH₃),

43.8 (CH₂), 63.6 (OCH₂CH₃), 114.0 (ArC), 125.8 (ArC), 127.0

(ArC), 128.1 (ArC), 128.6 (ArC), 129.5 (ArC), 129.6 (Csp²), 130.6

(ArC), 131.3 (ArC), 131.5 (ArC), 133.1 (ArC), 134.4 (Csp²), 135.3

(ArC), 159.7 (ArC), 166.9 (NHCO) ppm. HRMS (ES): m/z

calcd.for C₂₄H₂₂ClNNaO₂Se [M + Na]⁺494.0395; found 494.0406.

(E)-N-[3-Chloro-2-(phenylselanyl)allyl]benzamide (16Јib): Yield

35 mg (20%); yellowish oil. ¹H NMR (400 MHz, CDCl₃): δ = 4.45

3

4

(dd, J = 5.6, J = 1.2 Hz, 2 H, CH₂), 6.35 (br. s, 1 H, NH), 6.58

3

(t, J = 1.2 Hz, 1 H, CH), 7.26–7.29 (m, 3 H, ArH), 7.37 (t, J =

8.0 Hz, 2 H, ArH), 7.45–7.51 (m, 3 H, ArH), 7.59–7.62 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 41.0 (CH₂), 122.7

(Csp²), 127.0 (ArC), 128.2 (ArC), 128.4 (ArC), 128.5 (ArC), 129.7

(ArC), 130.8 (ArC), 131.6 (ArC), 133.0 (ArC), 134.0 (Csp²), 167.1

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₆H₁₄Cl³⁵NNaOSe

[M + Na] 373.9819; found 373.9826.

6-(3,4-Dimethoxyphenyl)-2-phenyl-5-(phenylselanyl)-4H-1,3-oxazine

(7cb): Yield 0.15 g (68 %); yellowish oil. ¹H NMR (400 MHz,

CDCl₃): δ = 3.85 (s, 3 H, OCH₃), 3.92 (s, 3 H, OCH₃), 4.31 (s, 2

3

H, CH₂), 6.92 (d, J = 8.0 Hz, 1 H, ArH), 7.21 (d, J = 2.0 Hz, 1

H, ArH), 7.24–7.29 (m, 4 H, ArH), 7.40 (t, ³J = 7.6 Hz, 2 H, ArH),

7.45–7.49 (m, 3 H, ArH), 7.97–7.99 (m, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 50.0 (CH₂), 56.00 (OCH₃), 56.01 (OCH₃),

99.7 (Csp²), 110.4 (ArC), 111.9 (ArC), 121.7 (ArC), 126.2 (ArC),

127.2 (ArC), 127.3 (ArC), 128.3 (ArC), 128.8 (ArC), 129.5 (ArC),

131.2 (ArC), 131.84 (ArC), 131.88 (ArC), 148.3 (Csp²), 149.8

(ArC), 150.0 (ArC), 159.9 (Csp²) ppm. HRMS (ESI): m/z calcd. for

C₂₄H₂₂NO₃Se [M + H] 452.0761; found 452.0756.

6-(4-Methoxyphenyl)-5-(phenylselanyl)-3,4-dihydro-2H-1,3-oxazin-

2-one (8ac): Yield 0.16 g (86%); yellow solid; m.p. 125–126 °C. IR

1

(KBr): ν

= 1742 (C=O), 3420 (NH) cm^–1. H NMR (400 MHz,

˜

max

3

CDCl₃): δ = 3.82 (s, 3 H, OCH₃), 3.99 (d, J = 1.2 Hz, 2 H, CH₂),

6.49 (br. s, 1 H, NH), 6.90 (d, J = 8.8 Hz, 2 H, ArH), 7.27–7.29

3

(m, 3 H, ArH), 7.41–7.43 (m, 2 H, ArH), 7.55 (t, ³J = 8.8 Hz, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 46.4 (CH₂), 55.3

(OCH₃), 97.3 (Csp²), 113.2 (ArC), 125.0 (ArC), 127.7 (ArC), 128.3

(ArC), 129.5 (ArC), 130.4 (ArC), 131.9 (ArC), 150.7 (Csp²), 151.4

(NHCO), 160.6 (ArC) ppm. HRMS (ESI): m/z calcd. for

C₁₇H₁₅NNaO₃Se [M + Na] 384.0110; found 384.0111.

(E)-N-[3-Chloro-3-(3,4-dimethoxyphenyl)-2-(phenylselanyl)allyl]-

benzamide (16cb): Yield 46.3 mg (19%); yellowish oil. ¹H NMR

(400 MHz, CDCl₃): δ = 3.84 (s, 3 H, OCH₃), 3.89 (s, 3 H, OCH₃), (E)-tert-Butyl 3-Chloro-3-(4-methoxyphenyl)-2-(phenylselanyl)allyl-

4.56 (d, ³J = 5.6 Hz, 2 H, CH₂), 6.37 (br. s, NH), 6.83 (d, ³J = carbamate (17ac): Yield 20.3 mg (9%); white oil. IR (KBr): ν

=

˜

max

8.4 Hz, 1 H, ArH), 6.93 (d, J = 2.0 Hz, 1 H, ArH), 7.00 (dd, J = 1714 (C=O), 3368 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

3

4

3

8.4, J = 2.0 Hz, 1 H, ArH), 7.24–7.26 (m, 3 H, ArH), 7.38–7.43

1.45 (s, 9 H, 3ϫCH₃), 3.84 (s, 3 H, OCH₃), 4.23 (d, J = 4.8 Hz,

(m, 4 H, ArH), 7.48 (tt, ³J = 7.6, J = 2.4 Hz, 1 H, ArH), 7.65–

2 H, CH₂), 4.84 (br. s, 1 H NH), 6.89 (d, J = 8.8 Hz, 2 H, ArH),

4

3

7.67 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 43.7 7.26–7.29 (m, 3 H, ArH), 7.35 (d, J = 8.8 Hz, 2 H, ArH), 7.40–

(CH₂), 56.00 (OCH₃), 56.03 (OCH₃), 110.4 (ArC), 112.1 (ArC), 7.43 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.3

122.0 (ArC), 126.1 (Csp²), 127.0 (ArC), 128.1 (ArC), 128.6 (ArC), (3ϫCH₃), 44.1 (CH₂), 55.2 (OCH₃), 79.4 [C(CH₃)₃], 113.3 (ArC),

129.5 (ArC), 129.6 (ArC), 131.6 (ArC), 133.0 (ArC), 134.3 (Csp²), 127.0 (Csp²), 127.8 (ArC), 129.3 (ArC), 129.5 (ArC), 130.4 (ArC),

139.4 (ArC), 148.4 (ArC), 148.8 (ArC), 166.9 (NHCO) ppm. 131.5 (ArC), 133.0 (ArC), 134.2 (Csp²), 155.2 (NHCO), 160.0

3

HRMS (ESI): m/z calcd. for C₂₄H₂₂Cl³⁵NNaO₃Se [M + Na]

(ArC) ppm. HRMS (ESI): m/z calcd. for C₂₁H₂₄³⁵ClNNaO₃Se [M

510.0344; found 510.0343.

+ Na] 476.0500; found 476.0504.

7104

www.eurjoc.org

Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

6-(3,4-Dimethoxyphenyl)-5-(phenylselanyl)-3,4-dihydro-2H-1,3-ox- (E)-tert-Butyl 3-Chloro-2-(phenylselanyl)-3-p-tolylallylcarbamate

azin-2-one (8bc): Yield 82.1 mg (42 %); yellow solid; m.p. 138– (17dc): Yield 67.7 mg (31%); yellowish oil. IR (KBr): ν

= 1715

˜

max

1

139 °C. IR (KBr): ν

= 1732 (C=O), 3239 (NH) cm^–1. H NMR (C=O), 3352 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.43 (s,

˜

max

3

(400 MHz, CDCl₃): δ = 3.84 (s, 3 H, OCH₃), 3.90 (s, 3 H, OCH₃), 9 H, 3ϫCH₃), 2.37 (s, 3 H, CH₃), 4.21 (d, J = 4.8 Hz, 2 H, CH₂),

3

3.99 (d, J = 1.2 Hz, 2 H, CH₂), 6.35 (br. s, 1 H, NH), 6.86 (d, J

4.81 (br. s, 1 H NH), 7.17 (d, ³J = 8.0 Hz, 2 H, ArH), 7.26–7.28

= 8.4 Hz, 1 H, ArH), 7.13 (d, J = 2.0 Hz, 1 H, ArH), 7.18 (dd, J (m, 5 H, ArH), 7.39–7.41 (m, 2 H, ArH) ppm. ¹³C NMR

= 8.4, ⁴J = 2.0 Hz, 1 H, ArH), 7.27–7.29 (m, 3 H, ArH), 7.42–7.44

(100 MHz, CDCl₃): δ = 21.3 (CH₃), 28.3 (3ϫCH₃), 44.0 (CH₂),

4

3

(m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 46.5 (CH₂), 79.4 [C(CH₃)₃], 127.3 (Csp²), 127.8 (ArC), 128.76 (ArC), 128.78

55.8 (OCH₃), 55.9 (OCH₃), 97.4 (CSe), 110.1 (ArC), 111.6 (ArC),

122.2 (ArC), 125.1 (ArC), 127.8 (ArC), 128.3 (ArC), 129.5 (ArC),

(ArC), 129.3 (ArC), 129.4 (ArC), 133.0 (ArC), 134.3 (Csp²), 136.3

(ArC), 139.1 (ArC), 155.2 (NHCO) ppm. HRMS (ESI): m/z calcd.

132.0 (ArC), 148.2 (ArC), 150.2 (ArC), 150.4 (Csp²), 151.3 for C₂₁H₂₄³⁵ClNNaO₂Se [M + Na] 460.0551; found 460.0549.

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₈H₁₇NNaO₄Se [M

+ Na] 414.0216; found 414.0216.

6-(4-Nitrophenyl)-5-(phenylselanyl)-3,4-dihydro-2H-1,3-oxazin-2-

one (8gc): Yield 18.8 mg (10%); yellow solid; m.p. 176–177 °C. IR

1

(KBr): ν

= 1732 (C=O), 3252 (NH) cm^–1. H NMR (400 MHz,

˜

(E)-tert-Butyl 3-Chloro-3-(3,4-dimethoxyphenyl)-2-(phenylselanyl)-

allylcarbamate (17bc): Yield 43.5 mg (18%); yellowish brown solid;

max

CDCl₃): δ = 4.05 (d, ³J = 1.6 Hz, 2 H, CH₂), 6.11 (br. s, 1 H, NH),

7.31–7.33 (m, 3 H, ArH), 7.42–7.45 (m, 2 H, ArH), 7.81 (d, ³J =

8.8 Hz, 2 H, ArH), 8.26 (d, ³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 46.7 (CH₂), 102.0 (Csp²), 123.2 (ArC),

127.1 (ArC), 128.5 (ArC), 129.8 (ArC), 129.9 (ArC), 132.6 (ArC),

138.5 (ArC), 148.0 (ArC), 148.2 (Csp²), 150.3 (NHCO) ppm.

HRMS (ESI): m/z calcd. for C₁₆H₁₂N₂NaO₄Se [M + Na] 398.9855;

found 398.9854.

m.p. 76–77 °C. IR (KBr): ν

= 1696 (C=O), 3403 (NH) cm^–1. ¹H

˜

max

NMR (400 MHz, CDCl₃): δ = 1.42 (s, 9 H, 3ϫCH₃), 3.82 (s, 3 H,

3

OCH₃), 3.89 (s, 3 H, OCH₃), 4.21 (d, J = 4.8 Hz, 2 H, CH₂), 4.82

(br. s, 1 H, NH), 6.82 (d, ³J = 8.4 Hz, 1 H, ArH), 6.87 (d, ⁴J =

2.0 Hz, 1 H, ArH), 6.96 (dd, ³J = 8.4, ⁴J = 2.0 Hz, 1 H, ArH),

7.23–7.25 (m, 3 H, ArH), 7.37–7.40 (m, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 28.4 (3 ϫ CH₃), 44.2 (CH₂), 55.9

(2 ϫ OCH₃), 79.5 [C(CH₃)₃], 110.3 (ArC), 112.0 (ArC), 121.9

(ArC), 127.2 (Csp²), 127.8 (ArC), 129.3 (ArC), 131.5 (ArC), 131.7

(ArC), 133.0 (ArC), 134.0 (Csp²), 148.3 (ArC), 149.6 (ArC), 155.3

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₂₂H₂₆³⁵ClNNaO₄Se

[M + Na] 506.0606; found 506.0601.

(E)-tert-Butyl 3-Chloro-3-(4-nitrophenyl)-2-(phenylselanyl)allylcarb-

amate (17gc): Yield 58.5 mg (25%); yellow oil. IR (KBr): ν

=

˜

max

1714 (C=O), 3430 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

3

1.44 (s, 9 H, 3ϫCH₃), 4.25 (d, J = 5.6 Hz, 2 H, CH₂), 4.87 (br. s,

1 H NH), 7.23–7.26 (m, 3 H, ArH), 7.30–7.33 (m, 2 H, ArH), 7.51

3

(d, J = 8.4 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ

6-(Benzo[d][1,3]dioxol-5-yl)-5-(phenylselanyl)-3,4-dihydro-2H-1,3-

= 28.3 (3ϫCH₃), 44.0 (CH₂), 79.7 [C(CH₃)₃], 123.4 (ArC), 123.5

(ArC), 128.1 (ArC), 129.1 (Csp²), 129.5 (ArC), 130.1 (ArC), 131.2

(Csp²), 132.9 (ArC), 145.3 (ArC), 147.5 (ArC), 155.3

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₂₀H₂₁³⁵ClN₂NaO₄Se

[M + Na] 491.0246; found 491.0253.

oxazin-2-one (8cc): Yield 0.11 g (56 %); yellow solid; m.p. 155–

1

156 °C. IR (KBr): ν

= 1748 (C=O), 3231 (NH) cm^–1. H NMR

˜

max

3

(400 MHz, CDCl₃): δ = 3.96 (d, J = 0.8 Hz, 2 H, CH₂), 5.99 (s, 2

H, OCH₂O), 6.62 (br. s, 1 H, NH), 6.81 (d, ³J = 8.4 Hz, 1 H, ArH),

7.07–7.09 (m, 2 H, ArH), 7.28–7.29 (m, 3 H, ArH), 7.41–7.43 (m,

2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 46.3 (CH₂),

98.0 (Csp²), 101.4 (OCH₂O), 107.7 (ArC), 109.1 (ArC), 123.5

(ArC), 126.3 (ArC), 127.9 (ArC), 128.0 (ArC), 129.5 (ArC), 132.2

(ArC), 147.2 (ArC), 148.7 (ArC), 150.0 (Csp²), 151.4

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₇H₁₃NNaO₄Se [M

+ Na] 397.9903; found 397.9901.

(E)-tert-Butyl 2-Chloro-3-(phenylselanyl)allylcarbamate (17Јhc):

Yield 0.13 g (75%); yellow oil. IR (KBr): ν_max= 1686 (C=O), 3301

˜

(NH) cm^{–1 1}H NMR (400 MHz, CDCl₃): δ = 1.41 (s, 9 H,

.

3ϫCH₃), 4.09 (d, ³J = 5.6 Hz, 2 H, CH₂), 4.80 (br. s, 1 H NH),

6.39 (br. s, 1 H Csp²H), 7.28–7.30 (m, 3 H, ArH), 7.47–7.50 (m, 2

H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.2 (3ϫCH₃),

41.2 (CH₂), 79.5 [C(CH₃)₃], 120.8 (Csp²Cl), 128.0 (ArC), 128.2

(ArC), 129.4 (ArC), 132.2 (Csp²), 133.2 (ArC), 155.3

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₄H₁₈³⁵ClNNaO₂Se

[M + Na] 370.0081; found 370.0081.

(E)-tert-Butyl 3-(Benzo[d][1,3]dioxol-5-yl)-3-chloro-2-(phenylselan-

yl)allylcarbamate (17cc): Yield 60.7 mg (26 %); yellow oil. IR

1

(KBr): ν

= 1710 (C=O), 3243 (NH) cm^–1. H NMR (400 MHz,

˜

max

CDCl₃): δ = 1.42 (s, 9 H, 3ϫCH₃), 4.17 (d, ³J = 5.2 Hz, 2 H, CH₂),

4.79 (br. s, 1 H, NH), 5.98 (s, 2 H, OCH₂O), 6.77 (d, J = 8.4 Hz,

3

N-[6-(4-Methoxyphenyl)-5-(phenylselanyl)-4H-1,3-oxazin-2-yl]-4-

methylbenzenesulfonamide (9ab): Yield 0.21 g (82%); white solid;

1 H, ArH), 6.85–6.86 (m, 2 H, ArH), 7.24–7.28 (m, 3 H, ArH),

7.39–7.41 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

28.3 (3ϫCH₃), 43.9 (CH₂), 79.4 [C(CH₃)₃], 101.4 (OCH₂O), 107.8

(ArC), 109.3 (ArC), 123.3 (ArC), 127.7 (Csp²), 127.9 (ArC), 129.2

(ArC), 129.3 (ArC), 132.8 (ArC), 133.2 (ArC), 134.3 (Csp²), 147.3

(ArC), 148.1 (ArC), 151.2 (NHCO) ppm. HRMS (ESI): m/z calcd.

for C₂₁H₂₂³⁵ClNNaO₄Se [M + Na] 490.0293; found 490.0293.

m.p. 218–222 °C. IR (KBr): ν

= 2997 (NH) cm^{–1 1}H NMR

.

˜

max

(400 MHz, [D₆]DMSO): δ = 2.33 (s, 3 H, CH₃), 3.81 (s, 3 H,

3

OCH₃), 3.86 (s, 2 H, CH₂), 7.01 (d, J = 8.8 Hz, 2 H, ArH), 7.25

(d, ³J = 8.0 Hz, 2 H, ArH), 7.30–7.38 (m, 3 H, ArH), 7.40–7.50

3

(m, 4 H, ArH), 7.63 (d, J = 8.2 Hz, 2 H, ArH), 9.17 (br. s, 1 H,

NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.4 (CH₃), 44.4

(CH₂), 55.8 (OCH₃), 99.8 (SeC-sp²), 113.9 (ArC), 123.8 (ArC),

126.6 (ArC), 128.1 (ArC), 128.4 (ArC), 129.6 (ArC), 130.3 (ArC),

130.9 (ArC), 132.2 (ArC), 140.9 (ArC), 142.4 (ArC), 148.7 (ArCC-

sp²), 153.1 (HNC-sp²), 161.0 (ArC) ppm. HRMS (ESI): m/z calcd.

for C₂₄H₂₃N₂O₄SSe [M + H] 515.0539; found 515.0536.

5-(Phenylselanyl)-6-p-tolyl-3,4-dihydro-2H-1,3-oxazin-2-one (8dc):

Yield 0.15 g (42%); yellow solid; m.p. 115–116 °C. IR (KBr): ν

˜

max

= 1752 (C=O), 3246 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

3

2.38 (s, 3 H, CH₃), 3.99 (d, J = 1.6 Hz, 2 H, CH₂), 6.44 (br. s, 1

H, NH), 7.20 (d, ³J = 8.0 Hz, 2 H, ArH), 7.28–7.30 (m, 3 H, ArH),

7.42–7.44 (m, 2 H, ArH), 7.49 (d, ³J = 8.0 Hz, 2 H, ArH) ppm. 6-(4-Methoxyphenyl)-N-phenyl-5-(phenylselanyl)-4H-1,3-oxazin-2-

¹³C NMR (100 MHz, CDCl₃): δ = 21.4 (CH₃), 46.4 (CH₂), 98.0 amine (9bb): Yield 0.2 g (92%); white solid; m.p. 166–170 °C. IR

(Csp²), 127.8 (ArC), 128.2 (ArC), 128.6 (ArC), 128.8 (ArC), 129.5 (KBr): ν

= 3426 (NH) cm^–1. ¹H NMR (400 MHz, [D₆]DMSO):

˜

max

(ArC), 129.7 (ArC), 132.1 (ArC), 140.0 (ArC), 150.8 (Csp²), 151.3 δ = 3.80 (s, 3 H, OCH₃), 4.02 (s, 2 H, CH₂), 7.03 (s, 2 H, CH₂),

3

(NHCO) ppm. HRMS (ESI): m/z calcd. for C₁₇H₁₅NNaO₂Se [M

+ Na] 368.0161; found 368.0158.

7.03 (d, J = 8.6 Hz, 2 H, ArH), 7.25–7.50 (m, 8 H, ArH), 7.51–

7.72 (m, 4 H, ArH), 11.87 (br. s, 1 H, NH) ppm. ¹³C NMR

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7105

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

(100 MHz, [D₆]DMSO): δ = 44.3 (CH₂), 55.8 (OCH₃), 100.7 (SeC- 7.25–7.38 (m, 4 H, ArH), 7.43–7.55 (m, 6 H, ArH), 11.53 (br. s, 1

sp²), 114.1 (ArC), 123.3 (ArC), 124.4 (ArC), 127.3 (ArC), 128.0

H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 49.0 (CH₂),

(ArC), 129.9 (ArC), 130.3 (ArC), 131.0 (ArC), 132.0 (ArC), 134.5 90.7 (SeC-sp²), 123.2 (ArC), 126.9 (ArC), 127.4 (ArC), 129.9

(ArC), 148.1 (ArCC-sp²), 154.0 (HNC-sp²), 161.2 (ArC) ppm. (ArC), 130.4 (2ϫArC), 130.5 (ArC), 135.1 (ArC), 154.5 (H₂CC-

HRMS (ESI): m/z calcd. for C₂₃H₂₁N₂O₂Se [M + H] 437.0764;

sp²), 158.5 (HNC-sp²) ppm. HRMS (ESI): m/z calcd. for

found 437.0760.

C₁₆H₁₅N₂OSe [M + H] 331.0345; found 331.0342.

N-[6-(3,4-Dimethoxyphenyl)-5-(phenylselanyl)-4H-1,3-oxazin-2-yl]-

4-methylbenzenesulfonamide (9db): Yield 0.2 g (73%); white solid;

(E)-N-Benzyl-5-[(phenylselanyl)methylene]-4,5-dihydrooxazol-2-

amine (14kb): Yield 68.8 mg (40%); white solid; m.p. 171–176 °C.

m.p. 153–154 °C. IR (KBr): ν

= 3285 (NH) cm^–1

.

¹H NMR IR (KBr): ν

= 3436(NH) cm^{–1 1}H NMR (400 MHz, [D₆]-

.

˜

max

(400 MHz, [D₆]DMSO): δ = 2.32 (s, 3 H, CH₃), 3.75 (s, 3 H, DMSO): δ = 4.60 (s, 2 H, CH₂), 4.66 (br. s, 2 H, HNCH₂), 6.63 (s,

3

OCH₃), 3.82 (s, 3 H, OCH₃), 3.86 (br. s, 2 H, CH₂), 7.03 (d, J = 1 H, CH), 7.25–7.44 (m, 6 H, ArH), 7.45–7.60 (m, 4 H, ArH),

4

8.4 Hz, 1 H, ArH), 7.13 (dd, ³J = 8.3, J = 2.2 Hz, 1 H,ArH), 7.25

11.16 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ

= 45.7 (HNCH₂), 47.8 (CH₂), 91.1 (SeC-sp²), 127.5 (ArC), 128.3

(2ϫArC), 129.0 (ArC), 130.0 (ArC), 130.4 (ArC), 130.6 (ArC),

(d, ³J = 8.3 Hz, 2 H, ArH), 7.31–7.39 (m, 4 H, ArH), 7.44–7.50

(m, 2 H, ArH), 7.65 (d, J = 8.2 Hz, 2 H, ArH), 9.22 (br. s, 1 H,

3

NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.3 (CH₃), 44.3 136.4 (ArC), 153.9 (H₂CC-sp²), 160.2 (HNC-sp²) ppm. HRMS

(CH₂), 55.9 (OCH₃), 56.0 (OCH₃), 100.0 (SeC-sp²), 111.3 (ArC), (ESI): m/z calcd. for C₁₇H₁₇N₂OSe [M + H]⁺345.0501; found

112.5 (ArC), 122.7 (ArC), 123.9 (ArC), 126.6 (ArC), 128.3 (ArC), 345.0501.

128.4 (ArC), 129.5 (ArC), 130.3 (ArC), 132.3 (ArC), 141.0 (ArC),

N-[6-(4-Methoxyphenyl)-5-(phenylselanyl)-4H-1,3-thiazin-2-yl]benz-

142.4 (ArC), 148.5 (ArC), 148.6 (ArCC-sp²), 150.7 (ArC), 153.6

amide (10ab): Yield 0.18 g (73%); yellow oil. IR (KBr): ν_max= 1681

˜

(HNC-sp²) ppm. HRMS (ESI): m/z calcd. for C₂₅H₂₄N₂NaO₅SSe

[M + Na] 567.0464; found 567.0461.

(C=O), 3196 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.84 (s,

3

3 H, OCH₃), 4.10 (s, 2 H, CH₂), 6.94 (d, J = 8.8 Hz, 2 H, ArH),

4-Methyl-N-[5-(phenylselanyl)-6-(p-tolyl)-4H-1,3-oxazin-2-yl]benz-

enesulfonamide (9fb): Yield 0.2 g (80 %); white solid; m.p. 224–

7.31–7.32 (m, 3 H, ArH), 7.39–7.41 (m, 3 H, ArH), 7.43–7.47 (m,

3 H, ArH), 7.49 (tt, ³J = 7.2, ⁴J = 1.2 Hz, 1 H, ArH), 7.15–7.17

226 °C. IR (KBr): ν

= 2918(NH) cm^–1. ¹H NMR (400 MHz, (m, 2 H, ArH), 10.84 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz,

˜

max

[D₆]DMSO): δ = 2.33 (s, 3 H, CH₃), 2.35 (s, 3 H, CH₃), 3.85 (s, 2 CDCl₃): δ = 49.8 (CH₂), 55.3 (OCH₃), 113.8 (ArC), 116.0 (Csp²),

H, CH₂), 7.21–7.29 (m, 4 H, ArH), 7.31–7.36 (m, 3 H, ArH), 7.36–

128.1 (2 ϫ ArC), 128.4 (ArC), 129.0 (ArC), 129.2 (ArC), 129.6

7.40 (m, 2 H, ArH), 7.41–7.47 (m, 2 H, ArH), 7.62 (d, ³J = 8.2 Hz,

(ArC), 130.9 (ArC), 132.1 (ArC), 133.2 (ArC), 134.2 (Csp²), 136.0

2 H), 9.16 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆]- (ArC), 160.4 (ArC), 168.4 (Csp²), 176.0 (CO) ppm. HRMS (ESI):

DMSO): δ = 21.4 (2ϫCH₃), 44.3 (CH₂), 100.8 (SeC-sp²), 126.6 m/z calcd. for C₂₄H₂₁N₂O₂SSe [M + H] 481.0484; found 481.0485.

(ArC), 127.9 (ArC), 128.5 (ArC), 128.8 (ArC), 129.0 (ArC), 129.1

N-[6-(4-Chlorophenyl)-5-(phenylselanyl)-4H-1,3-thiazin-2-yl]benz-

(ArC), 129.5 (ArC), 130.3 (ArC), 132.5 (ArC), 140.5 (ArC), 140.9

amide (10bb): Yield 50.8 mg (21%); white solid; m.p. 59–60 °C. IR

(ArC), 142.4 (ArC), 148.6 (ArCC-sp²), 153.1 (HNC-sp²) ppm.

1

(KBr): ν

= 1678 (C=O), 3173 (NH) cm^–1. H NMR (400 MHz,

˜

max

HRMS (ESI): m/z calcd. for C₂₄H₂₂N₂NaO₃SSe [M + Na]

521.0409; found 521.0417.

CDCl₃): δ = 4.13 (s, 2 H, CH₂), 7.33–7.34 (m, 3 H, ArH), 7.40

3

4

(br. s, 4 H, ArH), 7.42–7.47 (m, 4 H, ArH), 7.51 (tt, J = 7.6, J =

4-Methyl-N-[6-phenyl-5-(phenylselanyl)-4H-1,3-oxazin-2-yl]benz- 1.2 Hz, 1 H, ArH), 8.13–8.15 (m, 2 H, ArH), 10.73 (br. s, 1 H,

enesulfonamide (9gb): Yield 0.15 g (63%); white solid; m.p. 201–

NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 50.0 (CH₂), 118.0

204 °C. IR (KBr): ν

[D₆]DMSO): δ = 2.33 (s, 3 H, CH₃), 3.88 (s, 2 H, CH₂), 7.23 (d, J

= 3002 (NH) cm^–1. ¹H NMR (400 MHz, (Csp²), 128.2 (ArC), 128.4 (ArC), 128.5 (ArC), 128.8 (ArC), 129.2

˜

max

3

(ArC), 129.8 (ArC), 130.9 (ArC), 132.3 (ArC), 133.0 (ArC), 133.4

= 7.7 Hz, 2 H, ArH), 7.34 (br. s, 3 H, ArH), 7.48 (br. s, 7 H, ArH),

(ArC), 134.7 (Csp²), 135.6 (ArC), 135.8 (ArC), 167.6 (Csp²), 175.8

7.61 (d, ³J = 7.8 Hz, 2 H, ArH), 9.17 (br. s, 1 H, NH) ppm. ¹³C (CO) ppm. HRMS (ESI): m/z calcd. for C₂₃H₁₇³⁵ClN₂OSSe [M +

NMR (100 MHz, [D₆]DMSO): δ = 21.4 (CH₃), 44.3 (CH₂), 101.4 H] 484.9986; found 484.9988.

(SeC-sp²), 126.6 (ArC), 127.8 (ArC), 128.5 (ArC), 128.6 (ArC),

N-[6-Phenyl-5-(phenylselanyl)-4H-1,3-thiazin-2-yl]benzamide (10cb):

129.3 (ArC), 129.5 (ArC), 130.3 (ArC), 130.6 (ArC), 131.7 (ArC),

Yield 0.08 g (36%); yellow solid; m.p. 61–62 °C. IR (KBr): ν

=

˜

max

132.5 (ArC), 140.9 (ArC), 142.4 (ArC), 148.4 (ArCC-sp²), 153.0

(HNC-sp²) ppm. HRMS (ESI): m/z calcd. for C₂₃H₂₀N₂NaO₃SSe

[M + Na] 507.0252; found 507.0258.

1681 (C=O), 3193 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

4.13 (s, 2 H, CH₂), 7.30–7.34 (m, 3 H, ArH), 7.40–7.52 (m, 10 H,

ArH), 8.14–8.16 (m, 2 H, ArH), 10.86 (br. s, 1 H, NH) ppm. ¹³C

NMR (100 MHz, CDCl₃): δ = 49.8 (CH₂), 117.1 (Csp²), 128.1

(ArC), 128.2 (ArC), 128.5 (ArC), 128.8 (ArC), 129.2 (ArC), 129.5

(2ϫArC), 129.7 (ArC), 132.1 (ArC), 133.3 (ArC), 134.2 (Csp²),

(E)-N-{[2-Chloro-3-(phenylselanyl)allyl]carbamoyl}-4-methylbenz-

enesulfonamide (18Јib): Yield 0.21 g (94 %); off-white solid; m.p.

148–149 °C. IR (KBr): ν

= 1685 (C=O), 3301, 3317 (NH) cm^–1.

˜

max

¹H NMR (400 MHz, [D₆]DMSO): δ = 2.38 (s, 3 H, CH₃), 3.94 (d, 135.9 (ArC), 136.3 (ArC), 168.1 (Csp²), 175.9 (CO) ppm. HRMS

³J = 5.4 Hz, 2 H, CH₂), 6.61 (s, 1 H, CH), 6.70 (t, J = 5.6 Hz, 1 (ESI): m/z calcd. for C₂₃H₁₈N₂OSSe [M + H] 451.0378; found

3

H, NH), 7.27–7.35 (m, 3 H, ArH), 7.36–7.47 (m, 4 H, ArH), 7.77 451.0388.

(d, J = 8.2 Hz, 2 H, ArH), 10.64 (br. s, 1 H, NH) ppm. ¹³C NMR

3

(E)-N-[5-(Phenylselanylmethylene)-4,5-dihydrothiazol-2-yl]benz-

(100 MHz, [D₆]DMSO): δ = 21.5 (CH₃), 40.6 (CH₂), 121.5 (SeC-

amide (15db): Yield 74.8 mg (40%); yellow solid; m.p. 160–161 °C.

sp²), 127.7 (ArC), 128.4 (ArC), 129.1 (ArC), 129.9 (ArC), 130.1

IR (KBr): ν

= 1634 (C=O), 3410 (NH) cm^–1

.

¹H NMR

˜

max

(ArC), 132.4 (ArC), 133.0 (ClC-sp²), 137.7 (ArC), 144.1

(ArC), 151. 7 (CO) ppm. HRMS (ESI): m/z c alcd . for

C₁₇H₁₇ClN₂NaO₃SSe [M + Na] 466.9703, found 466.9704.

4

(400 MHz, [D₆]DMSO): δ = 4.45 (d, J = 2.8 Hz, 2 H, CH₂), 6.82

4

(t, J = 2.8 Hz, 1 H, CH), 7.26–7.30 (m, 1 H, ArH), 7.32–7.36 (m,

2 H, ArH), 7.45–7.50 (m, 4 H, ArH), 7.57 (tt, ³J = 7.6, ⁴J = 1.2 Hz,

1 H, ArH), 8.07–8.10 (m, 2 H, ArH), 10.43 (br. s, 1 H, NH) ppm.

¹³C NMR (100 MHz, [D₆]DMSO): δ = 51.9 (CH₂), 105.3 (Csp²H),

(E)-N-Phenyl-5-[(phenylselanyl)methylene]-4,5-dihydrooxazol-2-

amine (14jb): Yield 44.6 mg (27%); white solid; m.p. 160–165 °C.

IR (KBr): ν

= 3436 (NH) cm^–1

.

¹H NMR (400 MHz, [D₆]- 127.0 (ArC), 128.3 (ArC), 128.7 (ArC), 129.5 (ArC), 130.4 (ArC),

˜

max

DMSO): δ = 4.59 (d, J = 2.2 Hz, 2 H, CH₂), 6.66 (s, 1 H, CH), 130.5 (ArC), 132.2 (ArC), 135.0 (Csp²), 141.2 (ArC), 168.2 (Csp²),

4

7106

www.eurjoc.org

Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

172.3 (CO) ppm. HRMS (ESI): m/z calcd. for C₁₇H₁₄N₂OSSe [M NMR (100 MHz, CDCl₃): δ = 28.8 (CH₂), 42.7 (CH₂), 55.4

+ H] 375.0065; found 375.0072.

(OCH₃), 64.9 (CH₂), 75.2 (CH), 109.4 (Csp²), 114.0 (ArC), 125.2

(ArC), 126.6 (ArC), 127.0 (ArC), 127.3 (ArC), 128.3 (ArC), 129.0

(ArC), 130.0 (ArC), 131.0 (ArC), 131.9 (ArC), 134.6 (ArC), 135.1

(ArC), 147.4 (Csp²), 153.7 (Csp²), 160.4 (ArC) ppm. HRMS (ESI):

m/z calcd. for C₂₆H₂₅NNaO₄[M + Na] 438.1676; found 438.1674.

(E)-3-Chloro-3-(4-methoxyphenyl)-2-(phenylselanyl)allyl Tosyl-

carbamate (19ab): Yield 0.22 g (79%); colorless oil. IR (KBr): ν

˜

max

= 1697 (C=O), 3345 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

2.44 (s, 3 H, CH₃), 3.84 (s, 3 H, OCH₃),4.94 (s, 2 H, OCH₂), 6.90

(d, ³J = 8.8 Hz, 2 H, ArH), 7.18–7.23 (m, 3 H, ArH), 7.33–7.36

(m, 6 H, ArH), 7.96 (d, ³J = 8.4 Hz, 2 H, ArH), 8.25 (br. s, 1

H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.5 (CH₃), 55.2

(OCH₃), 66.7 (OCH₂), 113.4 (ArC), 122.6 (ArC or C-sp²), 126.3

(ArC or C-sp²), 128.1 (ArC or C-sp²), 128.3 (ArC or C-sp²), 129.2

(ArC or C-sp²), 129.5 (ArC or C-sp²), 130.3 (ArC or C-sp²), 130.7

(ArC or C-sp²), 133.7 (ArC or C-sp²), 135.4 (ArC or C-sp²), 135.9

(ArC or C-sp²), 144.9 (ArC or C-sp²), 149.8 (ArC), 160.2

(CO) ppm. HRMS (ESI): m/z calcd. for C₂₄H₂₂³⁵ClNNaO₅SSe [M

+ Na] 573.9970; found 573.9973.

5-[Methoxy(4-methoxyphenyl)methyl]-6-(4-methoxyphenyl)-2-

1

phenyl-4H-1,3-oxazine (7ad): Yield 0.11 g (51%); yellowish oil. H

NMR (400 MHz, CDCl₃): δ = 3.32 (s, 3 H, OCH₃), 3.80 (s, 3 H,

OCH₃), 3.86 (s, 3 H, OCH₃), 3.98 (d, ²J = 19.2 Hz, 1 H, CH₂),

2

3

4.22 (d, J = 19.2 Hz, 1 H, CH₂), 5.10 (s, 1 H, CH), 6.89 (d, J =

3

8.8 Hz, 2 H, ArH), 6.98 (d, J = 8.8 Hz, 2 H, ArH), 7.29 (d, J =

8.4 Hz, 2 H, ArH), 7.38 (t, J = 7.2 Hz, 2 H, ArH), 7.44 (t, J =

7.2 Hz, 1 H, ArH), 7.48 (d, J = 8.8 Hz, 2 H, ArH), 7.95–7.98 (m,

3

2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 42.0 (CH₂),

55.4 (OCH₃), 55.4 (OCH₃), 56.3 (OCH₃), 79.3 (CH), 108.7 (Csp²),

113.9 (ArC), 114.0 (ArC), 125.3 (ArC), 127.3 (ArC), 127.6 (ArC),

128.3 (ArC), 130.1 (ArC), 131.0 (ArC), 131.5 (ArC), 132.1 (ArC),

147.6 (Csp²), 153.5 (NCO), 159.1 (ArC), 160.3 (ArC) ppm. HRMS

(ESI): m/z calcd. for C₂₆H₂₆NO₄[M + H] 416.1856; found

416.1862.

(E)-3-Chloro-3-(4-methoxyphenyl)-2-(phenylselanyl)allyl Acetate

(20ab): Yield 0.15 g (78%); colorless oil. IR (KBr): ν

= 1712

˜

max

1

(C=O) cm^–1. H NMR (400 MHz, CDCl₃): δ = 2.02 (s, 3 H, CH₃),

3

3.85 (s, 3 H, OCH₃), 5.01 (s, 2 H, OCH₂), 6.92 (d, J = 8.8 Hz, 2

H, ArH), 7.28–7.30 (m, 3 H, ArH), 7.43 (d, ³J = 8.8 Hz, 2 H,

3

4

ArH), 7.47 (dd, J = 7.4, J = 2.0 Hz, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 20.7 (CH₃), 55.3 (OCH₃), 65.1 (OCH₂),

113.5 (ArC), 123.9 (ArC or C-sp²), 128.1 (ArC or C-sp²), 129.2

(ArC or C-sp²), 130.5 (ArC or C-sp²), 131.2 (ArC or C-sp²), 133.7

(ArC or C-sp²), 135.6 (ArC or C-sp²), 160.2 (ArC), 170.4

(CO) ppm. HRMS (ESI): m/z calcd. for C₁₈H₁₇³⁵ClNaO₃Se [M +

Na] 418.9922; found 418.9917.

(E)-N-[2-(4-Methoxybenzoyl)-3-(4-methoxyphenyl)allyl]benzamide

(23ad): Yield 22 mg (10%); yellowish oil. IR (KBr): ν

= 3334

˜

max

(NH), 1639 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.83 (s,

6 H, OCH₃), 3.87 (s, 3 H, OCH₃), 4.72 (d, ³J = 5.6 Hz, 2 H, CH₂),

3

6.95 (d, J = 8.8 Hz, 2 H, ArH), 6.97 (d, J = 8.4 Hz, 2 H, ArH),

7.16 (t, ³J = 5.6 Hz, 1 H, NH), 7.26 (s, 1 H, CH), 7.38 (t, ³J =

3

7.6 Hz, 2 H, ArH), 7.46 (t, J = 7.6 Hz, 1 H, ArH), 7.59 (d, J =

8.8 Hz, 2 H, ArH), 7.74–7.77 (m, 2 H, ArH), 7.80 (d, J = 8.8 Hz,

3

General Procedures for Oxocarbenium Ion Mediated Reactions

2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 38.2 (CH₂),

55.4 (OCH₃), 55.6 (OCH₃), 113.7 (ArC), 114.4 (ArC), 126.9 (ArC),

127.1 (ArC), 128.6 (ArC), 130.6 (ArC), 131.5 (ArC), 131.7 (ArC),

132.1 (ArC), 134.5 (ArC), 134.6 (Csp²), 143.7 (Csp²), 160.6 (ArC),

163.1 (ArC), 167.3 (NHCO), 198.7 (CO) ppm. HRMS (ESI): m/z

calcd. for C₂₅H₂₃NNaO₄[M + Na] 424.1519; found 424.1518.

Method A: To a mixture of 1, 3, 5 or 6 (0.5 mmol) and 1-methoxy-

isochromane (90.2 mg, 0.55 mmol) in anhydrous dichloromethane

(5 mL), trimethylsilyl triflate (0.09 mL, 0.5 mmol) was added either

at room temperature (for 1, 5, and 6) or at 0 °C (for 3). The re-

sulting solution was stirred at the same temperature.

Method B: To a cooled solution of 2 or 4 (0.5 mmol) and 1-meth-

oxyisochromane (90.2 mg, 0.55 mmol) in either anhydrous di-

chloromethane (5 mL, for 2) or anhydrous acetonitrile (5 mL, for

4) boron trifluoride etherate (0.06 mL, 0.5 mmol) was added at

0 °C. The resulting solution was stirred at the same temperature.

(Z)-N-[2-(4-Methoxybenzoyl)-3-(4-methoxyphenyl)allyl]benzamide

(24ad): Yield 23 mg (11%); yellowish oil. IR (KBr): ν

= 3326

˜

max

(NH), 1652 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.69 (s,

3

4

3 H, OCH₃), 3.77 (s, 3 H, OCH₃), 4.41 (d.d, J = 5.6, J = 0.8 Hz,

2 H, CH₂), 6.63 (d, ³J = 8.8 Hz, 2 H, ArH), 6.75–6.79 (m, 3 H,

ArH, NH), 6.94 (s, 1 H, CH), 7.08 (d, ³J = 8.8 Hz, 2 H, ArH), 7.39

Method C: To a cooled solution of 1 or 4 (0.5 mmol) and the corre-

sponding dialkoxymethylarene (0.75 mmol) in anhydrous dichloro-

methane (5 mL), boron trifluoride etherate (0.5 mmol, for 1) or

trimethylsilyl triflate (0.5 mmol, for 4) was added at –10 °C. The

resulting solution was stirred at the same temperature.

3

(t, J = 7.6 Hz, 2 H, ArH), 7.47 (t, J = 7.6 Hz, 1 H, ArH), 7.71–

7.73 (m, 2 H, ArH), 7.87 (d, ³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C

NMR (100 MHz, CDCl₃): δ = 45.5 (CH₂), 55.2 (OCH₃), 55.5

(OCH₃), 113.8 (ArC), 114.0 (ArC), 127.0 (ArC), 127.6 (ArC), 128.6

(ArC), 128.9 (ArC), 130.5 (ArC), 131.6 (ArC), 132.0 (ArC), 132.2

(ArC), 134.3 (ArC or Csp²), 134.4 (ArC or Csp²), 159.5 (ArC),

164.1 (ArC), 167.6 (NHCO), 199.2 (CO) ppm. HRMS (ESI): m/z

calcd. for C₂₅H₂₃NNaO₄[M + Na] 424.1519; found 424.1518.

Isolation Procedures for All Products: When completion of the reac-

tion was observed by TLC, the reaction was quenched with aque-

ous sodium hydrogen carbonate solution. The organic layer was

separated, washed with water (2ϫ20 mL), and dried with anhy-

drous Na₂SO₄. After the evaporation of solvent under reduced

pressure, the residue was purified by flash column chromatography

eluting with hexane/ethyl acetate mixtures.

5-[(4-Bromophenyl)(ethoxy)methyl]-6-(4-methoxyphenyl)-2-phenyl-

1

4H-1,3-oxazine (7ae): Yield 0.13 g (54%); yellowish oil. H NMR

(400 MHz, CDCl₃): δ = 1.23 (t, ³J = 7.2 Hz, 3 H, OCH₂CH₃), 3.32–

3.40 (m, 1 H, OCH₂CH₃), 3.56–3.64 (m, 1 H, OCH₂CH₃), 3.86 (s,

3 H, OCH₃), 3.92 (d, ²J = 19.2 Hz, 1 H, CH₂), 4.21 (d, ²J =

5-(Isochroman-1-yl)-6-(4-methoxyphenyl)-2-phenyl-4H-1,3-oxazine

(7ac): Yield 0.16 g (78 %); yellowish oil. ¹H NMR (400 MHz,

3

CDCl₃): δ = 2.63 (d, J = 16.4 Hz, 1 H, CH₂), 3.09–3.17 (m, 1 H,

19.2 Hz, 1 H, CH₂), 5.21 (s, 1 H, CH), 6.99 (d, J = 8.8 Hz, 2 H,

2

3

CH₂), 3.76–3.83 (m, 1 H, CH₂), 3.84 (d, J = 18.8 Hz, 1 H, CH₂), ArH), 7.27 (d, J = 8.4 Hz, 2 H, ArH), 7.38 (t, J = 7.6 Hz, 2 H,

3.85 (s, 3 H, OCH₃), 4.20 (d, J = 18.8 Hz, 1 H, CH₂), 4.21–4.26 ArH), 7.43–7.48 (m, 5 H, ArH), 7.95–7.97 (m, 2 H, ArH) ppm. ¹³

C

2

3

(m, 1 H, CH₂), 5.62 (s, 1 H, CH), 7.00 (d, J = 9.2 Hz, 2 H, ArH), NMR (100 MHz, CDCl₃): δ = 15.4 (OCH₂CH₃), 42.0 (CH₂), 55.4

7.10–7.15 (m, 2 H, ArH), 7.17–7.19 (m, 2 H, ArH), 7.40 (t, ³J =

(OCH₃), 64.0 (OCH₂CH₃), 77.2 (CH), 108.6 (Csp²), 114.1 (ArC),

121.4 (ArC), 125.2 (ArC), 127.3 (ArC), 128.1 (ArC), 128.3 (ArC),

3

4

7.6 Hz, 2 H, ArH), 7.46 (tt, J = 7.2, J = 2.8 Hz, 1 H, ArH), 7.64

(d, ³J = 8.8 Hz, 2 H, ArH), 8.00–8.03 (m, 2 H, ArH) ppm. ¹³C 130.1 (ArC), 131.0 (ArC), 131.6 (ArC), 132.0 (ArC), 139.0 (ArC),

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7107

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

147.7 (Csp²), 153.4 (NCO), 160.4 (ArC) ppm. HRMS (ESI): m/z

153.4 (Csp²) ppm. HRMS (ESI): m/z calcd. for C₂₇H₂₆NO₄[M +

H] 428.1856; found 428.1859.

calcd. for C₂₆H₂₅⁷⁹BrNO₃[M + H] 478.1018; found 478.1015.

(E)-N-[3-(4-Bromophenyl)-2-(4-methoxybenzoyl)allyl]benzamide 5-[(4-Bromophenyl)(ethoxy)methyl]-6-(3,4-dimethoxyphenyl)-2-

1

(23ae): Yield 33.7 mg (15%); yellowish oil. IR (KBr): ν

= 3332

phenyl-4H-1,3-oxazine (7ce): Yield 0.12 g (49%); yellowish oil. H

˜

max

(NH), 1645 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.86 (s, NMR (400 MHz, CDCl₃): δ = 1.23 (t, ³J = 6.8 Hz, 3 H,

3

3 H, OCH₃), 4.64 (d, J = 5.6 Hz, 2 H, CH₂), 6.95 (d, J = 8.8 Hz,

OCH₂CH₃), 3.34–3.41 (m, 1 H, OCH₂CH₃), 3.56–3.63 (m, 1 H,

3

2

2 H, ArH), 7.11 (t, J = 5.6 Hz, 1 H, NH), 7.16 (s, 1 H, CH), 7.37

(t, J = 7.6 Hz, 2 H, ArH), 7.45 (t, J = 7.2 Hz, 1 H, ArH), 7.50

(d, J = 8.4 Hz, 2 H, ArH), 7.57 (d, J = 8.4 Hz, 2 H, ArH), 7.71–

OCH₂CH₃), 3.87 (s, 3 H, OCH₃), 3.93 (s, 3 H, OCH₃), 3.94 (d, J

3

2

= 19.2 Hz, 1 H, CH₂), 4.22 (d, J = 19.2 Hz, 1 H, CH₂), 5.23 (s, 1

3

H, CH), 6.93 (d, J = 8.4 Hz, 2 H, ArH), 7.03 (d, J = 2.0 Hz, 1

3

7.73 (m, 2 H, ArH), 7.82 (d, ³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C H, ArH), 7.09 (d.d, J = 8.8, J = 2.0 Hz, 1 H, ArH), 7.26 (d, J

NMR (100 MHz, CDCl₃): δ = 38.1 (CH₂), 55.5 (OCH₃), 113.8 = 8.0 Hz, 2 H, ArH), 7.39 (t, ³J = 7.6 Hz, 2 H, ArH), 7.43–7.48

(ArC), 123.5 (ArC), 126.9 (ArC), 128.5 (ArC), 130.1 (ArC), 131.1

(ArC), 131.5 (ArC), 132.0 (ArC), 132.1 (ArC), 133.3 (ArC), 134.2

(m, 3 H, ArH), 7.95–7.98 (m, 2 H, ArH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 15.4 (OCH₂CH₃), 42.0 (CH₂), 56.0

(ArC), 137.5 (Csp²), 141.1 (Csp²), 163.4 (ArC), 167.3 (NHCO), (OCH₃), 56.1 (OCH₃), 64.1 (OCH₂CH₃), 77.3 (CH), 108.8 (Csp²),

198.0 (CO) ppm. HRMS (ESI): m/z calcd. for C₂₄H₂₀Br⁷⁹NNaO₃

[M + Na] 472.0519; found 472.0517.

111.0 (ArC), 111.7 (ArC), 121.5 (ArC), 121.6 (ArC), 125.3 (ArC),

127.3 (ArC), 128.2 (ArC), 128.3 (ArC), 131.1 (ArC), 131.6 (ArC),

138.9 (ArC), 147.6 (Csp²), 149.1 (ArC), 150.0 (ArC), 153.5

(NCO) ppm. HRMS (ESI): m/z calcd. for C₂₇H₂₇⁷⁹BrNO₄[M + H]

508.1123; found 508.1129.

(Z)-N-[3-(4-Bromophenyl)-2-(4-methoxybenzoyl)allyl]benzamide

(24ae): Yield 11.2 mg (5%); yellowish oil. IR (KBr): ν

= 3325

˜

max

(NH), 1647 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.79 (s,

4

3

3 H, OCH₃), 4.43 (dd, ³J = 5.8, J = 1.4 Hz, 2 H, CH₂), 6.71 (t, J

5-(Isochroman-1-yl)-2-phenyl-6-(3,4,5-trimethoxyphenyl)-4H-1,3-ox-

azine (7dc): Yield 0.25 g (54%); yellowish oil. ¹H NMR (400 MHz,

CDCl₃): δ = 2.63 (d, J = 16.4 Hz, 1 H, CH₂), 3.10–3.18 (m, 1 H,

3

= 5.2 Hz, 1 H, NH), 6.77 (d, J = 8.8 Hz, 2 H, ArH), 6.90 (s, 1 H,

3

CH), 7.01 (d, J = 8.4 Hz, 2 H, ArH), 7.23 (d, J = 8.4 Hz, 2 H,

3

ArH), 7.40 (t, J = 7.6 Hz, 2 H, ArH), 7.48 (t, J = 7.2 Hz, 1 H,

CH₂), 3.78–3.84 (m, 1 H, CH₂), 3.83 (d, J = 19.2 Hz, 1 H, CH₂),

ArH), 7.70–7.72 (m, 2 H, ArH), 7.85 (d, ³J = 9.2 Hz, 2 H, 3.90 (s, 6 H, 2ϫOCH₃), 3.90 (s, 3 H, OCH₃), 4.16 (d, ³J = 19.2 Hz,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 45.3 (CH₂), 55.6 1 H, CH₂), 4.23–4.28 (m, 1 H, CH₂), 5.64 (s, 1 H, CH), 6.94 (s, 2

(OCH₃), 114.2 (ArC), 122.3 (ArC), 127.0 (ArC), 128.6 (ArC), 128.7

H, ArH), 7.06–7.14 (m, 2 H, ArH), 7.15–7.18 (m, 2 H, ArH), 7.40

(ArC), 130.4 (ArC), 130.5 (ArC), 131.5 (ArC), 131.7 (ArC), 132.0 (t, ³J = 7.6 Hz, 2 H, ArH), 7.46 (tt, ³J = 7.2, ⁴J = 2.8 Hz, 1 H,

(ArC), 134.0 (ArC or Csp²), 134.2 (ArC or Csp²), 137.6 (Csp²),

ArH), 7.97–8.00 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

164.4 (ArC), 167.7 (NHCO), 198.5 (CO) ppm. HRMS (ESI): m/z

CDCl₃): δ = 28.8 (CH₂), 42.9 (CH₂), 56.3 (2 ϫ OCH₃), 61.0

calcd. for C₂₄H₂₀Br⁷⁹NNaO₃[M + Na] 472.0519; found 472.0514. (OCH₃), 64.9 (CH₂), 75.3 (CH), 105.9 (ArC), 109.8 (Csp²), 125.1

(ArC), 126.7 (ArC), 127.0 (ArC), 127.3 (ArC), 128.1 (ArC), 128.3

6-(4-Ethoxyphenyl)-5-(isochroman-1-yl)-2-phenyl-4H-1,3-oxazine

(ArC), 129.1 (ArC), 131.0 (ArC), 132.0 (ArC), 134.5 (ArC), 134.9

(7bc): Yield 0.11 g (53 %); yellowish oil. ¹H NMR (400 MHz,

(ArC), 139.0 (ArC), 148.9 (Csp²), 153.25 (Csp²), 159.29

(ArC) ppm. HRMS (ESI): m/z calcd. for C₂₈H₂₇NNaO₅[M + Na]

480.1781; found 480.1779.

3

CDCl₃): δ = 1.44 (t, J = 7.2 Hz, 3 H, OCH₂CH₃), 2.63 (d, J =

16.4 Hz, 1 H, CH₂), 3.09–3.17 (m, 1 H, CH₂), 3.76–3.82 (m, 1 H,

2

3

CH₂), 3.82 (d, J = 18.4 Hz, 1 H, CH₂), 4.08 (q, J = 7.2 Hz, 2 H,

2

OCH₂CH₃), 4.18 (d, J = 19.2 Hz, 1 H, CH₂), 4.21–4.25 (m, 1 H,

5-(Isochroman-1-yl)-2-phenyl-6-p-tolyl-4H-1,3-oxazine (7ec): Yield

CH₂), 5.61 (s, 1 H, CH), 6.97 (d, ³J = 8.8 Hz, 2 H, ArH), 7.10– 0.15 g (81%); yellowish oil. H NMR (400 MHz, CDCl₃): δ = 2.42

1

7.15 (m, 2 H, ArH), 7.16–7.19 (m, 2 H, ArH), 7.39 (t, J = 7.6 Hz, (s, 3 H, CH₃), 2.63 (d, ³J = 16.4 Hz, 1 H, CH₂), 3.09–3.17 (m, 1

3

4

3

2 H, ArH), 7.46 (tt, J = 7.2, J = 2.8 Hz, 1 H, ArH), 7.61 (d, J

H, CH₂), 3.75–3.81 (m, 1 H, CH₂), 3.83 (d, ³J = 18.8 Hz, 1 H,

= 8.8 Hz, 2 H, ArH), 7.98–8.03 (m, 2 H, ArH) ppm. ¹³C NMR

CH₂), 4.21 (d, J = 18.8 Hz, 1 H, CH₂), 4.21–4.25 (m, 1 H, CH₂),

3

(100 MHz, CDCl₃): δ = 14.9 (OCH₂CH₃), 28.8 (CH₂), 42.9 (CH₂), 5.61 (s, 1 H, CH), 7.10–7.15 (m, 2 H, ArH), 7.16–7.19 (m, 2 H,

3

63.6 (OCH₂CH₃), 64.9 (CH₂), 75.3 (CH), 109.3 (Csp²), 114.5

(ArC), 125.1 (ArC), 125.3 (ArC), 126.7 (ArC), 127.0 (ArC), 127.3

ArH), 7.28 (d, J = 7.6 Hz, 2 H, ArH), 7.40 (t, J = 7.6 Hz, 2 H,

ArH), 7.46 (tt, ³J = 7.2, ⁴J = 2.4 Hz, 1 H, ArH), 7.58 (d, ³J =

(ArC), 128.3 (ArC), 129.0 (ArC), 130.0 (ArC), 130.9 (ArC), 132.2 8.0 Hz, 2 H, ArH), 8.00–8.02 (m, 2 H, ArH) ppm. ¹³C NMR

(ArC), 134.7 (ArC), 135.3 (ArC), 148.6 (Csp²), 153.4 (Csp²), 169.8 (100 MHz, CDCl₃): δ = 21.5 (CH₃), 28.8 (CH₂), 42.7 (CH₂), 64.9

(ArC) ppm. HRMS (ESI): m/z calcd. for C₂₇H₂₆NO₃[M + Na]

412.1907; found 412.1914.

(CH₂), 75.2 (CH), 109.9 (Csp²), 125.2 (ArC), 126.7 (ArC), 127.0

(ArC), 127.4 (ArC), 128.3 (ArC), 128.5 (ArC), 129.0 (ArC), 129.3

(ArC), 129.9 (ArC), 131.1 (ArC), 131.8 (ArC), 134.7 (ArC), 135.1

(ArC), 139.5 (ArC), 148.6 (Csp²), 153.9 (ArC) ppm. HRMS (ESI):

m/z calcd. for C₂₆H₂₄NO₂[M + Na] 382.1802; found 382.1796.

6-(3,4-Dimethoxyphenyl)-5-(isochroman-1-yl)-2-phenyl-4H-1,3-ox-

1

azine (7cc): Yield 0.15 g (70%); yellowish oil. H NMR (400 MHz,

3

CDCl₃): δ = 2.62 (d, J = 16.4 Hz, 1 H, CH₂), 3.08–3.17 (m, 1 H,

3

CH₂), 3.76–3.82 (m, 1 H, CH₂), 3.83 (d, J = 19.2 Hz, 1 H, CH₂), 5-[Methoxy(4-methoxyphenyl)methyl]-2-phenyl-6-p-tolyl-4H-1,3-ox-

3.92 (s, 6 H,2ϫOCH₃), 4.17 (d, ³J = 19.2 Hz, 1 H, CH₂), 4.21–

azine (7ed): Yield 93.7 mg (47 %); yellowish oil. ¹H NMR

3

4.26 (m, 1 H, CH₂), 5.62 (s, 1 H, CH), 6.94 (d, J = 8.0 Hz, 2 H, (400 MHz, CDCl₃): δ = 2.42 (s, 3 H, CH₃), 3.33 (s, 3 H, OCH₃),

2

ArH), 7.08–7.14 (m, 2 H, ArH), 7.15–7.18 (m, 2 H, ArH), 7.23–

3.80 (s, 3 H, OCH₃), 3.99 (d, J = 19.2 Hz, 1 H, CH₂), 4.24 (d, J

3

7.28 (m, 2 H, ArH), 7.39 (t, J = 7.6 Hz, 2 H, ArH), 7.46 (t, J = = 19.2 Hz, 1 H, CH₂), 5.11 (s, 1 H, CH), 6.89 (d, ³J = 8.8 Hz, 2

7.2 Hz, 1 H, ArH), 7.99–8.01 (m, 2 H, ArH) ppm. ¹³C NMR H, ArH), 7.26–7.30 (m, 4 H, ArH), 7.38 (t, ³J = 7.6 Hz, 2 H, ArH),

(100 MHz, CDCl₃): δ = 28.8 (CH₂), 42.8 (CH₂), 56.04 (OCH₃), 7.42–7.46 (m, 3 H, ArH), 7.96–7.98 (m, 2 H, ArH) ppm. ¹³C NMR

56.07 (OCH₃), 64.9 (CH₂), 75.3 (CH), 109.4 (Csp²), 110.9 (ArH), (100 MHz, CDCl₃): δ = 21.5 (CH₃), 41.9 (CH₂), 55.4 (OCH₃), 56.3

111.7 (ArC), 125.2 (ArC), 125.4 (ArC), 126.6 (ArC), 127.0 (ArC), (OCH₃), 79.2 (CH), 109.1 (Csp²), 113.9 (ArC), 127.3 (ArC), 127.5

127.3 (ArC), 128.3 (ArC), 129.0 (ArC), 130.9 (ArC), 132.1 (ArC), (ArC), 128.3 (ArC), 128.7 (ArC), 129.3 (ArC), 130.1 (ArC), 130.9

134.6 (ArC), 135.1 (ArC), 148.7 (Csp²), 148.9 (ArC), 150.0 (ArC), (ArC), 131.4 (ArC), 132.1 (ArC), 139.4 (ArC), 147.8 (Csp²), 153.5

7108

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Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

(NCO), 159.1 (ArC) ppm. HRMS (ESI): m/z calcd. for C₂₆H₂₆NO₃

[M + H] 400.1907; found 400.1914.

2 H, ArH), 7.71–7.75 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

CDCl₃): δ = 21.7 (CH₃), 38.0 (CH₂), 127.1 (ArC), 128.6 (ArC),

128.9 (ArC), 129.2 (ArC), 129.4 (ArC), 129.7 (ArC), 129.9 (ArC),

131.5 (ArC), 134.4 (ArC), 134.5 (ArC), 135.2 (ArC), 136.8 (Csp²),

143.3 (ArC), 144.4 (ArC), 167.3 (NHCO), 199.5 (CO) ppm. HRMS

(ESI): m/z calcd. for C₂₄H₂₁NNaO₂[M + Na] 378.1465; found

378.1467.

(E)-N-[3-(4-Methoxyphenyl)-2-(4-methylbenzoyl)allyl]benzamide

(23ed): Yield 21.2 mg (11%); yellowish oil. IR (KBr): ν

= 3342

˜

max

(NH),1638 (C=O) cm^–1. H NMR (400 MHz, CDCl₃): δ = 2.43 (s,

1

3

3 H, CH₃), 3.83 (s, 3 H, OCH₃), 4.74 (d, J = 5.6 Hz, 2 H, CH₂),

3

6.97 (d, J = 8.8 Hz, 2 H, ArH), 7.13 (t, J = 5.2 Hz, 1 H, NH),

7.27 (d, ³J = 8.0 Hz, 2 H, ArH),7.31 (s, 1 H, CH), 7.40 (t, ³J =

5-(Isochroman-1-yl)-2,6-diphenyl-4H-1,3-oxazine (7fc): Yield 0.14 g

3

1

2

7.6 Hz, 2 H, ArH), 7.47 (t, J = 7.2 Hz, 1 H, ArH), 7.60 (d, J = (78%); yellowish oil. H NMR (400 MHz, CDCl₃): δ = 2.63 (d, J

8.4 Hz, 2 H, ArH), 7.68 (d, J = 8.4 Hz, 2 H, ArH), 7.75–7.78 (m, = 16.4 Hz, 1 H, CH₂), 3.14 (ddd, ²J = 17.3, ³J = 11.7 Hz, ²J =

3

2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.7 (CH₃), 6.0 Hz, 1 H, CH₂), 3.79 (td, ^2,3J = 11.6, J = 3.2 Hz, 1 H, CH₂),

3

38.0 (CH₂), 55.5 (OCH₃), 114.4 (ArC), 126.9 (ArC), 127.1 (ArC), 3.86 (d, ²J = 19.2 Hz, 1 H, CH₂), 4.23 (d, ²J = 19.2 Hz, 1 H, CH₂),

128.6 (ArC), 129.2 (ArC), 129.8 (ArC), 131.5 (ArC), 131.9 (ArC), 4.22–4.27 (m, 1 H, CH₂), 5.63 (s, 1 H, CH), 7.11–7.15 (m, 2 H,

134.6 (ArC or Csp²), 134.6 (ArC or Csp²), 135.5 (ArC), 143.0

(ArC), 144.9 (Csp²), 160.8 (ArC), 167.3 (NHCO), 199.8 (CO) ppm.

HRMS (ESI): m/z calcd. for C₂₅H₂₃NNaO₃[M + Na] 408.1570;

found 408.1574.

ArH), 7.17–7.20 (m, 2 H, ArH), 7.38–7.24 (m, 2 H, ArH), 7.44–

7.51 (m, 4 H, ArH), 7.69–7.22 (m, 2 H, ArH), 8.00–8.02 (m, 2 H,

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.8 (CH₂), 42.8

(CH₂), 64.9 (CH₂), 75.1 (CH), 110.2 (Csp²), 125.2 (ArC), 126.6

(ArC), 127.0 (ArC), 127.3 (ArC), 128.2 (ArC), 128.6 (2ϫArC),

129.0 (ArC), 129.4 (ArC), 130.9 (ArC), 132.0 (ArC), 132.8 (ArC),

134.6 (ArC), 135.1 (ArC), 148.6 (Csp²), 153.4 (Csp²) ppm. HRMS

(ESI): m/z calcd. for C₂₅H₂₂NO₂[M + Na] 368.1645; found

368.1651.

5-[(4-Bromophenyl)(ethoxy)methyl]-2-phenyl-6-p-tolyl-4H-1,3-

oxazine (7ee): Yield 0.11 g (48 %); yellowish oil. ¹H NMR

(400 MHz, CDCl₃): δ = 1.23 (t, ³J = 6.8 Hz, 3 H, OCH₂CH₃), 2.42

(s, 3 H, CH₃), 3.32–3.40 (m, 1 H, OCH₂CH₃), 3.92 (d, ²J = 19.2 Hz,

1 H, CH₂), 4.21 (d, ²J = 19.6 Hz, 1 H, CH₂), 5.21 (s, 1 H, CH),

7.26–7.29 (m, 4 H, ArH), 7.36–7.48 (m, 8 H, ArH), 7.95–7.97 (m,

5-[(4-Bromophenyl)(ethoxy)methyl]-2,6-diphenyl-4H-1,3-oxazine

2 H, ArH) ppm. ^{1 3}C NMR (100 MHz, CDCl₃): δ = 15.4 (7fe): Yield 0.12 g (54 %); solid; m.p. 89–90 °C. ¹H NMR

(OCH₂CH₃), 21.5 (CH₃), 41.9 (CH₂), 64.0 (OCH₂CH₃), 77.1 (CH), (400 MHz, CDCl₃): δ = 1.22 (t, ³J = 7.2 Hz, 3 H, OCH₂CH₃), 3.32–

109.0 (Csp²), 121.4 (ArC), 127.3 (ArC), 128.1 (ArC), 128.3 (ArC), 3.39 (m, 1 H, OCH₂CH₃), 3.56–3.64 (m, 1 H, OCH₂CH₃), 3.93 (d,

128.6 (ArC), 129.4 (ArC), 130.0 (ArC), 131.0 (ArC), 131.6 (ArC), ²J = 19.2 Hz, 1 H, CH₂), 4.22 (d, J = 19.2 Hz, 1 H, CH₂), 5.20 (s,

2

132.0 (ArC), 138.9 (ArC), 139.5 (ArC), 147.9 (Csp²), 153.5 1 H, CH), 7.26 (d, J = 8.4 Hz, 2 H, ArH), 7.38 (t, J = 7.6 Hz, 2

3

(NCO) ppm. HRMS (ESI): m/z calcd. for C₂₆H₂₅⁷⁹BrNO₂[M + H] H, ArH), 7.43–7.48 (m, 6 H, ArH), 7.52–7.54 (m, 2 H, ArH), 7.94–

462.1069; found 462.1070.

7.97 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 15.4

(OCH₂CH₃), 41.9 (CH₂), 64.0 (OCH₂CH₃), 77.1 (CH), 109.4

(Csp²), 121.5 (ArC), 127.3 (ArC), 128.1 (ArC), 128.3 (ArC), 128.7

(ArC), 128.8 (ArC), 129.5 (ArC), 131.1 (ArC), 131.5 (ArC), 131.9

(ArC), 132.8 (ArC), 138.9 (ArC), 147.8 (Csp²), 153.4 (NCO) ppm.

HRMS (ESI): m/z calcd. for C₂₅H₂₃⁷⁹BrNO₂[M + H] 448.0912;

found 448.0911.

(E)-N-[3-(4-Bromophenyl)-2-(4-methylbenzoyl)allyl]benzamide

(23ee): Yield 49.8 mg (22%); yellowish oil. IR (KBr): ν

= 3341

˜

max

(NH), 1645 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.42 (s,

3

4

3

3 H, CH₃), 4.66 (dd, J = 6.0, J = 0.4 Hz, 2 H, CH₂), 7.10 (t, J

3

= 5.2 Hz, 1 H, NH), 7.22 (s, 1 H, CH), 7.27 (d, J = 8.8 Hz, 2 H,

3

ArH), 7.38 (t, J = 7.6 Hz, 2 H, ArH), 7.46 (t, J = 7.2 Hz, 1 H,

3

ArH), 7.51 (d, J = 8.4 Hz, 2 H, ArH), 7.57 (d, J = 8.4 Hz, 2 H,

(E)-N-[2-Benzoyl-3-(4-bromophenyl)allyl]benzamide (23fe): Yield

ArH), 7.68 (d, ³J = 8.4 Hz, 2 H, ArH), 7.72–7.74 (m, 2 H,

12.6 mg (6%); yellowish oil. ¹H NMR (400 MHz, CDCl₃): δ = 4.67

ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.7 (CH₃), 38.0 (dd, ³J = 6.0, ⁴J = 0.8 Hz, 2 H, CH₂), 7.05 (t, J = 5.6 Hz, 1 H,

3

(CH₂), 123.7 (ArC), 127.0 (ArC), 128.6 (ArC), 129.3 (ArC), 129.9

(ArC), 131.2 (ArC), 131.6 (ArC), 132.1 (ArC), 133.3 (ArC), 134.3

NH), 7.25 (s, 1 H, CH), 7.40 (t, J = 7.6 Hz, 2 H, ArH), 7.45–7.49

3

(m, 3 H, ArH), 7.53 (d, J = 8.4 Hz, 2 H, ArH), 7.56–7.60 (m, 3

(ArC), 135.1 (ArC), 137.6 (Csp²), 142.5 (Csp²), 143.5 (ArC), 167.4 H, ArH), 7.73–7.78 (m, 4 H, ArH) ppm. ¹³C NMR (100 MHz,

(NHCO), 199.2 (CO) ppm. HRMS (ESI): m/z calcd. for CDCl₃): δ = 37.9 (CH₂), 123.9 (ArC), 127.1 (ArC), 128.6 (ArC),

C₂₄H₂₀Br⁷⁹NNaO₂[M + Na] 456.0570; found 456.0577.

128.7 (ArC), 129.7 (ArC), 131.3 (ArC), 131.7 (ArC), 132.2 (ArC),

132.6 (ArC), 133.2 (ArC), 134.3 (ArC), 137.5 (ArC or Csp²), 137.9

(ArC or Csp²), 143.4 (Csp²), 167.4 (NHCO) ppm. HRMS (ESI):

m/z calcd. for C₂₃H₁₉⁷⁹BrNO₂[M + H] 420.0599; found 420.0597.

5-[Methoxy(phenyl)methyl]-2-phenyl-6-p-tolyl-4H-1,3-oxazine (7ef):

1

Yield 0.09 g (50%); yellowish oil. H NMR (400 MHz, CDCl₃): δ

2

= 2.44 (s, 3 H, CH₃), 3.36 (s, 3 H, OCH₃), 3.97 (d, J = 19.2 Hz, 1

H, CH₂), 4.25 (d, ²J = 19.2 Hz, 1 H, CH₂), 5.17 (s, 1 H, CH), 7.27– 5-[(4-Bromophenyl)(ethoxy)methyl]-6-(4-chlorophenyl)-2-phenyl-4H-

7.30 (m, 3 H, ArH), 7.34–7.45 (m, 7 H, ArH), 7.47 (d, ³J = 8.0 Hz,

1,3-oxazine (7ge): Yield 0.13 g (52 %); yellowish oil. ¹H NMR

2 H, ArH), 7.96–7.99 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, (400 MHz, CDCl₃): δ = 1.23 (t, ³J = 6.8 Hz, 3 H, OCH₂CH₃), 3.32–

CDCl₃): δ = 21.5 (CH₃), 41.9 (CH₂), 56.3 (OCH₃), 79.5 (CH), 109.0 3.39 (m, 1 H, OCH₂CH₃), 3.54–3.61 (m, 1 H, OCH₂CH₃), 3.92 (d,

(Csp²), 126.3 (ArC), 127.3 (ArC), 127.6 (ArC), 128.3 (ArC), 128.5 ²J = 19.2 Hz, 1 H, CH₂), 4.22 (d, J = 19.6 Hz, 1 H, CH₂), 5.14 (s,

2

3

(ArC), 128.7 (ArC), 129.4 (ArC), 130.1 (ArC), 130.9 (ArC), 132.1 1 H, CH), 7.24 (d, J = 8.0 Hz, 2 H, ArH), 7.39 (t, J = 7.6 Hz, 2

(ArC), 139.4 (ArC), 139.4 (ArC), 148.0 (Csp²), 153.4 (NCO) ppm.

HRMS (ESI): m/z calcd. for C₂₅H₂₄NO₂[M + H] 370.1807; found

370.1809.

H, ArH), 7.44–7.49 (m, 7 H, ArH), 7.92–7.95 (m, 2 H, ArH) ppm.

¹³C NMR (100 MHz, CDCl₃): δ = 15.3 (OCH₂CH₃), 42.0 (CH₂),

64.1 (OCH₂CH₃), 77.1 (CH), 110.1 (Csp²), 121.6 (ArC), 127.3

(ArC), 128.1 (ArC), 128.3 (ArC), 129.1 (ArC), 130.0 (ArC), 131.1

(ArC), 131.1 (ArC), 131.7 (ArC), 131.8 (ArC), 135.5 (ArC), 138.5

(ArC), 146.7 (Csp²), 153.1 (NCO) ppm. HRMS (ESI): m/z calcd.

for C₂₅H₂₂⁷⁹Br³⁵ClNO₂[M + H] 482.0522; found 482.0523.

(E)-N-[2-(4-Methylbenzoyl)-3-phenylallyl]benzamide (23ef): Yield

17.8 mg (10%); yellowish oil. IR (KBr): ν

= 3254 (NH), 1645

˜

max

(C=O) cm^–1. H NMR (400 MHz, CDCl₃): δ = 2.43 (s, 3 H, CH₃),

1

3

4

3

4.72 (dd, J = 6.0, J = 0.4 Hz, 2 H, CH₂), 7.11 (t, J = 5.2 Hz, 1

3

H, NH), 7.28 (d, J = 8.0 Hz, 2 H, ArH), 7.33 (s, 1 H, CH), 7.37– (E)-N-[3-(4-Bromophenyl)-2-(4-chlorobenzoyl)allyl]benzamide

7.40 (m, 3 H, ArH), 7.43–7.48 (m, 2 H, ArH), 7.61 (d, ³J = 7.2 Hz, (23ge): Yield 27.2 mg (11%); yellowish oil. ¹H NMR (400 MHz,

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7109

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

CDCl₃): δ = 4.65 (d, J = 5.2 Hz, 2 H, CH₂), 7.00 (t, J = 4.8 Hz, CH₂), 3.75 (td, ^2,3J = 11.6, J = 3.2 Hz, 1 H, CH₂), 3.99 (dd, J =

3

2

1 H, NH), 7.19 (s, 1 H, CH), 7.39 (t, ³J = 7.6 Hz, 2 H, ArH), 7.43– 14.8, J = 1.2 Hz, 1 H, CH₂), 4.18–4.22 (m, 1 H, CH₂), 5.47 (br. s,

3

7.49 (m, 3 H, ArH), 7.52 (d, J = 8.4 Hz, 2 H, ArH), 7.59 (d, J = 1 H, NH), 5.55 (s, 1 H, CH), 7.05–7.08 (m, 1 H, ArH), 7.10–7.14

8.8 Hz, 2 H, ArH), 7.71–7.73 (m, 4 H, ArH) ppm. ¹³C NMR (m, 1 H, ArH), 7.19–7.21 (m, 2 H, ArH), 7.22 (d, ³J = 8.4 Hz, 2 H,

3

(100 MHz, CDCl₃): δ = 37.9 (CH₂), 124.1 (ArC), 127.0 (ArC),

ArH), 7.51 (d, J = 8.0 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

128.7 (ArC), 128.9 (ArC), 131.1 (ArC), 131.3 (ArC), 131.7 (ArC),

CDCl₃): δ = 21.4 (CH₃), 28.6 (CH₂), 40.1 (CH₂), 64.9 (CH₂), 74.8

132.2 (ArC), 133.0 (ArC), 134.2 (ArC), 136.1 (ArC), 137.7 (Csp²), (CH), 108.6 (Csp²), 125.1 (ArC), 126.7 (2 ϫ ArC), 127.2 (ArC),

139.1 (ArC), 143.1 (Csp²), 167.5 (NHCO), 198.2 (CO) ppm. 128.5 (ArC), 128.9 (ArC), 129.1 (ArC), 134.4 (ArC), 134.7 (ArC),

HRMS (ESI): m/z calcd. for C₂₃H₁₇Br⁷⁹Cl³⁵NNaO₂[M + Na]

139.8 (ArC), 149.4 (Csp²), 151.1 (NHCO) ppm. HRMS (ESI): m/z

476.0023; found 476.0022.

calcd. for C₂₀H₁₉NNaO₃[M + Na] 344.1257; found 344.1258.

5-(Isochroman-1-yl)-6-(4-nitrophenyl)-2-phenyl-4H-1,3-oxazine 5-(Isochroman-1-yl)-6-phenyl-3,4-dihydro-2H-1,3-oxazin-2-one

(7hc): Yield 28.8 mg (14%); yellowish oil. ¹H NMR (400 MHz,

CDCl₃): δ = 2.66 (d, J = 16.4 Hz, 1 H, CH₂), 3.05–3.18 (m, 1 H,

(8ed): Yield 61.3 mg (40 %); white solid; m.p. 189–190 °C. IR

3

1

(KBr): ν

= 1751 (C=O), 3255 (NH) cm^–1. H NMR (400 MHz,

˜

max

3

2

CH₂), 3.79 (td, ^2,3J = 11.4, J = 3.2 Hz, 1 H, CH₂), 3.85 (d, J =

CDCl₃): δ = 2.60 (d, J = 16.4 Hz, 1 H, CH₂), 3.02–3.11 (m, 1 H,

19.6 Hz, 1 H, CH₂), 4.20 (d, ³J = 19.2 Hz, 1 H, CH₂), 4.24–4.27 CH₂), 3.55 (dd, J = 14.8, J = 1.6 Hz, 1 H, CH₂), 3.74 (td, ^2,3J =

2

3

2

3

(m, 1 H, CH₂), 5.54 (s, 1 H, CH), 7.01–7.03 (m, 1 H, ArH), 7.14– 11.4, J = 3.2 Hz, 1 H, CH₂), 3.99 (dd, J = 14.8, J = 1.2 Hz, 1

3

7.21 (m, 3 H, ArH), 7.41 (t, J = 7.2 Hz, 2 H, ArH), 7.48 (t, J = H, CH₂), 4.20 (ddd, ²J = 11.4, ³J = 6.0 Hz, ³J = 1.2 Hz, 1 H, CH₂),

3

7.6 Hz, 1 H, ArH), 7.87 (d, J = 8.8 Hz, 2 H, ArH), 7.94–7.96 (m, 5.54 (s, 1 H, CH), 6.11 (br. s, 1 H, NH), 7.05–7.07 (m, 1 H, ArH),

2 H, ArH), 8.33 (d, ³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C NMR 7.10–7.13 (m, 1 H, ArH), 7.18–7.21 (m, 2 H, ArH), 7.41–7.43 (m,

(100 MHz, CDCl₃): δ = 28.7 (CH₂), 42.9 (CH₂), 64.9 (CH₂), 74.8 3 H, ArH), 7.61–7.63 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz,

(CH), 113.2 (Csp²), 123.9 (ArC), 124.9 (ArC), 126.8 (ArC), 127.3 CDCl₃): δ = 28.5 (CH₂), 40.0 (CH₂), 64.8 (CH₂), 74.6 (CH), 109.1

(ArC), 127.3 (ArC), 128.4 (ArC), 129.3 (ArC), 129.5 (ArC), 131.3 (Csp²), 125.0 (ArC), 126.7 (ArC), 127.2 (ArC), 128.4 (ArC), 128.6

(ArC), 131.6 (ArC), 134.3 (ArC), 134.6 (ArC), 139.0 (ArC), 146.5

(Csp²), 148.2 (ArC), 152.7 (Csp²) ppm. HRMS (ESI): m/z calcd. (ArC), 149.2 (Csp²), 151.3 (NHCO) ppm. HRMS (ESI): m/z calcd.

for C₂₅H₂₀N₂NaO₄[M + Na] 435.1315; found 435.1314. for C₁₉H₁₇NNaO₃[M + Na] 330.1101; found 330.1101.

(ArC), 129.1 (ArC), 129.6 (ArC), 131.8 (ArC), 134.4 (ArC), 134.5

5-(Isochroman-1-yl)-6-(4-methoxyphenyl)-3,4-dihydro-2H-1,3-ox- 6-(4-Chlorophenyl)-5-(isochroman-1-yl)-3,4-dihydro-2H-1,3-oxazin-

azin-2-one (8ad): Yield 59 mg (35%); white solid; m.p. 170–171 °C.

2-one (8fd): Yield 49.5 mg (29%); white solid; m.p. 71–172 °C. IR

1

IR (KBr): ν

= 1749 (C=O), 3266 (NH) cm^{–1 1}H NMR (KBr): ν

.

= 1747 (C=O), 3278 (NH) cm^–1. H NMR (400 MHz,

˜

max

(400 MHz, CDCl₃): δ = 2.60 (d, ²J = 16.4 Hz, 1 H, CH₂), 3.01–

CDCl₃): δ = 2.60 (d, J = 16.4 Hz, 1 H, CH₂), 2.90–2.99 (m, 1 H,

2

3

2

3

3.10 (m, 1 H, CH₂), 3.52 (dd, J = 14.8, J = 1.6 Hz, 1 H, CH₂),

CH₂), 3.29 (dd, J = 15.2, J = 1.6 Hz, 1 H, CH₂), 3.68 (td, ^2,3J =

3.74 (td, ^2,3J = 11.6, J = 2.8 Hz, 1 H, CH₂), 3.82 (s, 3 H, OCH₃), 11.2, J = 3.2 Hz, 1 H, CH₂), 3.75 (dd, J = 15.2, J = 1.2 Hz, 1

3

2

3

2

3

2

3

3.95 (dd, J = 14.8, J = 1.6 Hz, 1 H, CH₂), 4.19 (ddd, J = 10.0, H, CH₂), 4.10 (dd, J = 11.4, J = 4.8 Hz, 1 H, CH₂), 5.34 (s, 1 H,

3

³J = 6.0 Hz, J = 1.2 Hz, 1 H, CH₂), 5.53 (s, 1 H, CH), 6.33 (br. s, CH), 7.06–7.12 (m, 1 H, ArH), 7.15–7.22 (m, 3 H, ArH), 7.57 (br. s,

1 H, NH), 6.92 (d, ³J = 8.8 Hz, 2 H, ArH), 7.04–7.06 (m, 1 H,

ArH), 7.10–7.12 (m, 1 H, ArH), 7.16–7.19 (m, 2 H, ArH), 7.55 (d,

³J = 8.8 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ =

4 H, ArH), 7.81 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz,

CDCl₃): δ = 27.9 (CH₂), 39.1 (CH₂), 64.1 (CH₂), 74.0 (CH), 110.0

(Csp²), 124.9 (ArC), 126.6 (ArC), 127.1 (ArC), 128.8 (ArC), 129.1

28.5 (CH₂), 39.9 (CH₂), 55.2 (OCH₃), 64.8 (CH₂), 74.7 (CH), 108.2 (ArC), 130.2 (ArC), 130.7 (ArC), 134.3 (ArC), 137.6 (ArC), 134.4

(Csp²), 113.7 (ArC), 124.2 (ArC), 125.0 (ArC), 126.6 (ArC), 127.1 (ArC), 147.6 (Csp²), 149.7 (NHCO) ppm. HRMS (ESI): m/z calcd.

(ArC), 129.0 (ArC), 130.0 (ArC), 134.4 (ArC), 134.6 (ArC), 149.0 for C₁₉H₁₆³⁵ClNNaO₃[M + Na] 364.0711; found 364.0704.

(Csp²), 151.6 (NHCO), 160.6 (ArC) ppm. HRMS (ESI): m/z calcd.

N-[5-(Isochroman-1-yl)-6-(4-methoxyphenyl)-4H-1,3-oxazin-2-yl]-

for C₂₀H₁₉NNaO₄[M + Na] 360.1206; found 360.1206.

4-methylbenzenesulfonamide (9ac): Yield 0.18 g (74%); white solid;

6-(3,4-Dimethoxyphenyl)-5-(isochroman-1-yl)-3,4-dihydro-2H-1,3- m.p. 246 °C. IR (KBr): ν

= 3145 (NH) cm^{–1 1}H NMR

.

˜

max

oxazin-2-one (8bd): Yield 0.1 g (55 %); yellow solid; m.p. 168–

(400 MHz, [D₆]DMSO): δ = 2.34 (s, 3 H, CH₃), 2.61 (m, 1 H,

1

170 °C. IR (KBr): ν

= 1750 (C=O), 3334 (NH) cm^–1. H NMR ArCCH₂), 2.95 (m, 1 H, ArCCH₂), 3.33 (m, 1 H, NCH₂), 3.66 (m,

˜

max

(400 MHz, CDCl₃): δ = 2.60 (d, ²J = 15.6 Hz, 1 H, CH₂), 3.01–

1 H, OCH₂), 3.73 (m, 1 H, NCH₂), 3.82 (s, 3 H, OCH₃), 4.10 (m,

3.10 (m, 1 H, CH₂), 3.53 (d, ²J = 14.8 Hz, 1 H, CH₂), 3.75 (td, ^2,3J 1 H, OCH₂), 5.41 (s, 1 H, CH), 7.03 (d, J = 6.6 Hz, 1 H, ArH),

3

= 11.6, J = 3.2 Hz, 1 H, CH₂), 3.88 (s, 3 H, OCH₃), 3.89 (s, 3 H, 7.07 (d, J = 8.7 Hz, 2 H, ArH), 7.15–7.23 (m, 3 H, ArH), 7.25 (d,

2

3

OCH₃), 3.95 (d, J = 14.4 Hz, 1 H, CH₂), 4.20 (dd, ²J = 11.2, J = ³J = 8.0 Hz, 2 H, ArH), 7.44 (d, J = 8.6 Hz, 2 H, ArH), 7.63 (d,

6.0 Hz, 1 H, CH₂), 5.56 (s, 1 H, CH), 6.13 (br. s, 1 H, NH), 6.87 ³J = 8.1 Hz, 2 H, ArH), 9.11 (s, 1 H, NH) ppm. ¹³C NMR

(d, ³J = 8.4 Hz, 1 H, ArH), 7.03–7.06 (m, 1 H, ArH), 7.09–7.12

(100 MHz, [D₆]DMSO): δ = 21.4 (CH₃), 28.3 (ArCCH₂), 38.1

(m, 1 H, ArH), 7.16–7.20 (m, 4 H, ArH) ppm. ¹³C NMR (NCH₂), 55.8 (OCH₃), 64.6 (OCH₂), 74.2 (CH), 110.5 (H₂CC-sp2),

(100 MHz, CDCl₃): δ = 28.5 (CH₂), 40.0 (CH₂), 55.8 (OCH₃), 55.9 114.5 (ArC), 122.8 (ArC), 125.3 (ArC), 126.6 (ArC), 127.1 (ArC),

(OCH₃), 64.8 (CH₂), 74.8 (CH), 108.3 (Csp²), 110.5 (ArC), 111.5

127.2 (ArC), 129.5 (ArC), 129.6 (ArC), 130.4 (ArC), 134.3 (ArC),

(ArC), 121.5 (ArC), 124.3 (ArC), 125.0 (ArC), 126.6 (ArC), 127.1 134.9 (ArC), 141.0 (ArC), 142.3 (ArC), 147.8 (C-sp²), 153.5 (HNC-

(ArC), 129.1 (ArC), 134.3 (ArC), 134.5 (ArC), 148.7 (ArC), 149.3

sp²), 160.9 (ArC) ppm. HRMS (ESI): m/z calcd. for C₂₇H₂₇N₂O₅S

(Csp²), 150.1 (ArC), 151.5 (NHCO) ppm. HRMS (ESI): m/z calcd. [M + H]⁺491.1635; found 491.1639.

for C₂₁H₂₁NNaO₅[M + Na] 390.1312; found 390.1308.

N-[6-(3,4-Dimethoxyphenyl)-5-(isochroman-1-yl)-4H-1,3-oxazin-2-

5-(Isochroman-1-yl)-6-p-tolyl-3,4-dihydro-2H-1,3-oxazin-2-one yl]-4-methylbenzenesulfonamide (9dc): Yield 0.23 g (88 %); white

1

(8dd): Yield 78.6 mg (49 %); white solid; m.p. 141–142 °C. IR

needles; m.p. 141 °C. IR (KBr): ν

= 3300 (NH) cm^–1. H NMR

˜

max

1

(KBr): ν

= 1751 (C=O), 3271 (NH) cm^–1. H NMR (400 MHz, (400 MHz, [D₆]DMSO): δ = 2.32 (s, 3 H, CH₃), 2.61 (d, ³J =

˜

max

2

CDCl₃): δ = 2.38 (s, 3 H, CH₃), 2.60 (d, J = 15.6 Hz, 1 H, CH₂), 16.2 Hz, 1 H, ArCCH₂), 2.90–3.00 (m, 1 H, ArCCH₂), 3.28–3.34

3.02–3.11 (m, 1 H, CH₂), 3.55 (dd, ²J = 14.6, ³J = 1.6 Hz, 1 H, (m, 1 H, NCH₂), 3.68–3.73 (m, 1 H, OCH₂), 3.74–3.76 (m, 1 H,

7110

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Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

3

NCH₂), 3.80 (s, 3 H, OCH₃), 3.81 (s, 3 H, OCH₃), 4.11 (ddd, J =

11.1, ³J = 5.8 Hz, ²J = 1.5 Hz, 1 H, OCH₂), 5.50 (s, 1 H, CH),

7.00–7.12 (m, 3 H, ArH), 7.16–7.26 (m, 5 H, ArH), 7.30 (br. s, 1

H, ArH), 7.64 (d, ³J = 8.0 Hz, 2 H), 9.13 (br. s, 1 H, NH) ppm.

¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.3 (CH₃), 28.3 (ArCCH₂),

38.1 (NCH₂), 55.9 (OCH₃), 56.0 (OCH₃), 64.6 (OCH₂), 74.2 (CH),

110.6 (H₂CC-sp²), 111.9 (ArC), 112.3 (ArC), 121.8 (ArC), 122.9

N-[5-(Isochroman-1-yl)-6-(4-methoxyphenyl)-4H-1,3-thiazin-2-yl]-

benzamide (10ad): Yield 0.19 g (82%); yellow solid; m.p. 78–79 °C.

IR (KBr): ν

= 1676 (C=O), 3198 (NH) cm^{–1 1}H NMR

.

˜

max

(400 MHz, CDCl₃): δ = 2.63 (d, ²J = 15.2 Hz, 1 H, CH₂), 3.10–

3

3.18 (m, 1 H, CH₂), 3.72 (td, ^2,3J = 11.6, J = 3.2 Hz, 1 H, CH₂),

2

3.77 (d, J = 15.2 Hz, 1 H, CH₂), 3.83 (s, 3 H, OCH₃), 3.96 (d, J

2

3

= 15.2 Hz, 1 H, CH₂), 4.22 (ddd, J = 11.2, J = 5.6, J = 0.8 Hz,

(ArC), 125.3 (ArC), 126.6 (ArC), 127.1 (ArC), 127.7 (ArC), 129.5 1 H, CH₂), 5.51 (s, 1 H, CH), 6.96–6.98 (m, 3 H, ArH), 7.13–7.21

(ArC), 129.6 (ArC), 134.4 (ArC), 134.9 (ArC), 141.1 (ArC), 142.2 (m, 3 H, ArH), 7.38–7.42 (m, 2 H, ArH), 7.46–7.50 (m, 1 H, ArH),

(ArC), 148.1 (ArCC-sp²), 149.0 (ArC), 150.7 (ArC), 153.6 (HNC- 7.53 (d, ³J = 8.8 Hz, 2 H, ArH), 8.17–8.20 (m, 2 H, ArH), 11.0

sp²) ppm. HRMS (ESI): m/z calcd. for C₂₈H₂₉N₂O₆S [M + H]⁺

521.1741; found 521.1746.

(br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.5

(CH₂), 43.7 (CH₂), 55.3 (OCH₃), 64.8 (CH₂), 75.7 (CH), 114.2

(ArC), 125.2 (ArC), 126.7 (ArC), 126.8 (ArC), 127.3 (ArC), 127.4

(Csp²), 128.0 (ArC), 129.1 (ArC), 129.3 (ArC), 130.8 (ArC), 131.9

(ArC), 134.2 (ArC), 134.9 (ArC), 135.3 (Csp²), 136.5 (ArC), 160.4

(ArC), 169.5 (Csp²), 176.7 (CO) ppm. HRMS (ESI): m/z calcd. for

C₂₇H₂₅N₂O₃S [M + H] 457.1580; found 457.1585.

N-[5-(Isochroman-1-yl)-6-(p-tolyl)-4H-1,3-oxazin-2-yl]-4-methyl-

benzenesulfonamide (9fc): Yield 0.23 g (92%); white solid; m.p. 259–

261 °C. IR (KBr): ν

= 3300 (NH) cm^–1. ¹H NMR (400 MHz,

˜

max

3

[D₆]DMSO): δ = 2.34 (s, 3 H, CH₃), 2.37 (s, 3 H, CH₃), 2.60 (d, J

= 16.4, Hz, 1 H, ArCCH₂), 2.89–3.00 (m, 1 H, ArCCH₂), 3.29–

3.33 (m, 1 H, NCH₂), 3.67 (td, ³J = 11.5, ²J = 3.0 Hz, 1 H, OCH₂),

N-[6-(4-Chlorophenyl)-5-(isochroman-1-yl)-4H-1,3-thiazin-2-yl]-

benzamide (10bd): Yield 0.13 g (55%); yellow solid; m.p. 56–57 °C.

3

2

3

3.74 (dd, J = 15.3, J = 1.1 Hz, 1 H, NCH₂), 4.09 (dd, J = 11.1,

²J = 5.6 Hz, 1 H, OCH₂), 5.40 (s, 1 H, CH), 7.02 (d, J = 6.5 Hz,

IR (KBr): ν

= 1679 (C=O), 3197 (NH) cm^{–1 1}H NMR

.

3

˜

max

1 H, ArH), 7.15–7.28 (m, 5 H, ArH), 7.31 (d, ³J = 8.1 Hz, 2 H,

(400 MHz, CDCl₃): δ = 2.64 (d, ²J = 16.0 Hz, 1 H, CH₂), 3.10–

ArH), 7.36 (d, ³J = 8.2 Hz, 2 H, ArH), 9.10 (s, 1 H, NH) ppm. ¹³

C

3.18 (m, 1 H, CH₂), 3.73 (td, J = 11.6, J = 2.8 Hz, 1 H, CH₂),

2

3

NMR (100 MHz, [D₆]DMSO): δ = 21.3 (CH₃), 21.4 (CH₃), 28.3 3.78 (d, ²J = 15.2 Hz, 1 H, CH₂), 3.96 (d, ²J = 15.6 Hz, 1 H, CH₂),

(ArCCH₂), 38.1 (NCH₂), 64.6 (OCH₂), 74.1 (CH), 111.1 (H₂CC- 4.22 (dd, ²J = 11.4, ³J = 5.2 Hz, 1 H, CH₂), 5.44 (s, 1 H, CH), 6.91

sp²), 125.3 (ArC), 126.6 (ArC), 127.1 (ArC), 127.7 (ArC), 127.8

(d, ³J = 7.2 Hz, 1 H, ArH), 7.13–7.25 (m, 4 H, ArH), 7.39–7.42

3

(ArC), 129.5 (ArC), 129.6 (ArC), 129.7 (ArC), 134.2 (ArC), 134.9 (m, 4 H, ArH), 7.52 (d, J = 8.8 Hz, 2 H, ArH), 8.15–8.17 (m, 2

(ArC), 140.4 (ArC), 141.0 (ArC), 142.3 (ArC), 147.8 (ArCC-sp²), H, ArH), 10.9 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃):

1 5 3 . 4 ( H N C - s p ²) p p m . H R M S ( E S I ) : m / z c a l c d . fo r

δ = 28.5 (CH₂), 43.9 (CH₂), 64.9 (CH₂), 75.6 (CH), 125.1 (ArC),

126.4 (ArC), 126.8 (ArC), 127.2 (ArC), 127.4 (Csp²), 128.1 (ArC),

128.9 (ArC), 129.1 (ArC), 129.2 (ArC), 129.3 (ArC), 130.8 (ArC),

132.0 (ArC), 133.2 (ArC), 134.3 (ArC), 134.5 (ArC), 135.5 (Csp²),

164.8 (Csp²), 174.2 (CO) ppm. HRMS (ESI): m/z calcd. for

C₂₆H₂₁³⁵ClN₂O₂S [M + H] 461.1085; found 461.1095.

C₂₇H₂₆N₂NaO₄S [M + Na]⁺497.1505; found 497.1500.

N-[5-(Isochroman-1-yl)-6-phenyl-4H-1,3-oxazin-2-yl]-4-methylbenz-

enesulfonamide (9gc): Yield 0.21 g (90%); white solid; m.p. 225–

226 °C. IR (KBr): ν

= 3152 (NH) cm^–1. ¹H NMR (400 MHz,

˜

max

[D₆]DMSO): δ = 2.34 (s, 3 H, CH₃), 2.61 (d, ³J = 16.4 Hz, 1 H,

ArCCH₂), 2.95 (m, 1 H, ArCCH₂), 3.35 (d, ²J = 15.4 Hz, 1 H, N-[5-(Isochroman-1-yl)-6-phenyl-4H-1,3-thiazin-2-yl]benzamide

3

2

NCH₂), 3.68 (td, J = 11.4, J = 8.7 Hz, 1 H, OCH₂), 3.77 (d, J (10cd): Yield 0.14 g (64%); white solid; m.p. 89–90 °C. IR (KBr):

= 15.4 Hz, 1 H, NCH₂), 4.10 (td, ³J = 10.0, ²J = 5.4 Hz, 1 H,

ν

_max= 1682 (C=O), 3189 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃):

˜

3

OCH₂), 5.41 (s, 1 H, CH), 7.04 (d, J = 6.3 Hz, 1 H, ArH), 7.14–

δ = 2.62 (d, ²J = 15.2 Hz, 1 H, CH₂), 3.09–3.18 (m, 1 H, CH₂),

7.29 (m, 5 H, ArH), 7.45–7.56 (m, 5 H, ArH), 7.61 (d, ³J = 8.1 Hz,

3.72 (td, J = 11.6, J = 3.2 Hz, 1 H, CH₂), 3.80 (d, J = 15.2 Hz,

2

3

2

2 H, ArH), 9.11 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, [D₆] 1 H, CH₂), 3.99 (d, J = 15.2 Hz, 1 H, CH₂), 4.22 (ddd, J = 11.2,

2

DMSO): δ = 21.4 (CH₃), 28.3 (ArCCH₂), 38.2 (NCH₂), 64.6 ³J = 5.4, J = 1.2 Hz, 1 H, CH₂), 5.49 (s, 1 H, CH), 6.97 (d, J =

3

(OCH₂), 74.1 (CH), 111.6 (H₂CC-sp²), 125.3 (ArC), 126.6 (ArC),

127.1 (ArC), 127.8 (ArC), 128.9 (ArC), 129.1 (ArC), 129.5 (ArC),

129.6 (ArC), 130.6 (ArC), 134.1 (ArC), 134.9 (ArC), 141.0 (ArC),

7.2 Hz, 1 H, ArH), 7.13–7.21 (m, 3 H, ArH), 7.39–7.49 (m, 6 H,

ArH), 7.58–7.60 (m, 2 H, ArH), 8.18–8.20 (m, 2 H, ArH), 10.9

(br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 28.5

142.3 (ArC), 147.7 (ArCC-sp²), 153.4 (HNC-sp²) ppm. HRMS (CH₂), 43.7 (CH₂), 64.8 (CH₂), 75.6 (CH), 125.2 (ArC), 126.7

(ESI): m/z calcd. for C₂₆H₂₅N₂O₄S [M + H]⁺461.1530; found

(ArC), 127.3 (ArC), 128.0 (ArC), 128.1 (Csp²), 128.8 (ArC), 129.1

(ArC), 129.2 (ArC), 129.3 (ArC), 129.4 (ArC), 131.9 (ArC), 134.2

(ArC), 134.7 (2ϫArC), 135.2 (Csp²), 136.4 (ArC), 169.1 (Csp²),

176.5 (CO) ppm. HRMS (ESI): m/z calcd. for C₂₆H₂₂N₂O₂S [M +

H] 427.1475; found 427.1484.

461.1536.

N-[6-(4-Chlorophenyl)-5-(isochroman-1-yl)-4H-1,3-oxazin-2-yl]-4-

methylbenzenesulfonamide (9hc): Yield 0.15 g (62 %); white solid;

m.p. 275–277 °C. IR (KBr): ν

= 3124 (NH) cm^{–1 1}H NMR

.

˜

max

(400 MHz, [D₆]DMSO): δ = 2.34 (s, 3 H, CH₃), 2.61 (d, ³J = N-{5-[Methoxy(4-methoxyphenyl)methyl]-6-(4-methoxyphenyl)-4H-

3

16.2 Hz, 1 H, ArCCH₂), 2.88–2.99 (m, 1 H, ArCCH₂), 3.69 (d, J

= 11.6 Hz, 1 H, OCH₂), 3.75 (d, J = 15.6 Hz, 1 H, NCH₂), 4.05– m.p. 47–48 °C. IR (KBr): ν

1,3-thiazin-2-yl}benzamide (10ae): Yield 0.18 g (76%); yellow solid;

3

= 1680 (C=O), 3194 (NH) cm^–1. ¹H

˜

max

3

4.15 (m, 1 H, OCH₂), 5.38 (s, 1 H, CH), 7.03 (d, J = 6.02 Hz, 1 NMR (400 MHz, CDCl₃): δ = 3.30 (s, 3 H, OCH₃), 3.81 (s, 3 H,

H, ArH), 7.15–7.30 (m, 5 H, ArH), 7.35–7.45 (m, 1 H, ArH), 7.46– OCH₃), 3.84 (s, 3 H, OCH₃), 3.89 (d, ²J = 15.2 Hz, 1 H, CHH),

2

3

7.55 (m, 2 H, ArH), 7.56–7.67 (m, 4 H, ArH), 9.12 (br. s, 1 H,

4.08 (d, J = 15.2 Hz, 1 H, CHH), 5.03 (s, 1 H, CH), 6.89 (d, J =

NH) ppm. ¹³C NMR (100 MHz, [D₆]DMSO): δ = 21.4 (CH₃), 28.3 8.8 Hz, 2 H, ArH), 6.94 (d, J = 8.8 Hz, 2 H, ArH), 7.22 (d, J =

3

(ArCCH₂), 38.3 (NCH₂), 64.5 (OCH₂), 73.9 (CH), 112.3 (H₂CC- 8.0 Hz, 2 H, ArH), 7.38 (d, J = 8.8 Hz, 2 H, ArH), 7.41 (d, J =

sp²), 125.4 (ArC), 126.6 (ArC), 127.1 (ArC), 127.8 (ArC), 129.3

(ArC), 129.5 (ArC), 129.6 (ArC), 130.7 (ArC), 133.5 (ArC), 134.0

(ArC), 134.9 (ArC), 135.4 (ArC), 141.0 (ArC), 142.4 (ArC), 146.7

7.6 Hz, 2 H, ArH), 7.48 (tt, ³J = 7.2, ⁴J = 1.2 Hz, 1 H, ArH),

8.18–8.20 (m, 2 H, ArH), 11.07 (br. s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 42.4 (CH₂), 55.2 (OCH₃), 55.3 (OCH₃),

(ArC), (ArCC-sp²), 153.2 (HNC-sp²) ppm. HRMS (ESI): m/z 56.6 (OCH₃), 79.4 (CH), 114.0 (ArC), 114.3 (ArC), 126.8 (ArC),

calcd. for C₂₆H₂₄ClN₂O₄S [M + H] 495.1140; found 495.1143.

127.2 (ArC), 127.9 (Csp²), 128.0 (ArC), 129.4 (ArC), 130.8 (ArC),

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7111

ˇ

A. Urbanaite, M. Jonusˇis, R. Buksˇnaitiene, S. Balkaitis, I. Cikotiene

˙

FULL PAPER

131.1 (ArC), 131.9 (ArC), 134.0 (Csp²), 136.5 (ArC), 159.2 (ArC), (CO) ppm. HRMS (ESI): m/z calcd. for C₂₆H₂₂³⁵Cl⁷⁹BrN₂O₂S [M

160.3 (ArC), 170.0 (Csp²), 176.8 (CO) ppm. HRMS (ESI): m/z

+ H] 540.0274; found 540.0271.

calcd. for C₂₇H₂₇N₂O₄S [M + H] 475.1686; found 475.1687.

N-{5-[Methoxy(4-methoxyphenyl)methyl]-6-phenyl-4H-1,3-thiazin-

2-yl}benzamide (10ce): Yield 0.18 g (81%); yellow oil. IR (KBr):

N-{5-[(4-Bromophenyl)(ethoxy)methyl]-6-(4-methoxyphenyl)-4H-

1,3-thiazin-2-yl}benzamide (10af): Yield 0.16 g (59%); yellow solid;

ν

_max= 1680 (C=O), 3198 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃):

˜

δ = 3.31 (s, 3 H, OCH₃), 3.80 (s, 3 H, OCH₃), 3.91 (d, ²J = 15.6 Hz,

m.p. 89–90 °C. IR (KBr): ν

= 1684 (C=O), 3203 (NH) cm^–1. ¹H

˜

max

2

1 H, CHH), 4.09 (d, J = 15.2 Hz, 1 H, CHH), 5.01 (s, 1 H, CH),

NMR (400 MHz, CDCl₃): δ = 1.21 (t, ³J = 7.2 Hz, 3 H,

3

6.89 (d, J = 8.8 Hz, 2 H, ArH), 7.21 (d, J = 7.6 Hz, 2 H, ArH),

7.38–7.46 (m, 7 H, ArH), 7.48 (tt, ³J = 7.6, ⁴J = 1.2 Hz, 1 H, ArH),

8.18–8.20 (m, 2 H, ArH), 11.03 (br. s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 42.4 (CH₂), 55.2 (OCH₃), 56.5 (OCH₃),

79.3 (CH), 114.0 (ArC), 127.1 (ArC), 128.0 (ArC), 128.5 (Csp²),

128.8 (ArC), 129.2 (ArC), 129.3 (ArC), 129.4 (ArC), 130.9 (ArC),

132.0 (ArC), 133.9 (Csp²), 134.7 (ArC), 136.3 (ArC), 159.1 (ArC),

169.4 (Csp²), 176.6 (CO) ppm. HRMS (ESI): m/z calcd. for

C₂₆H₂₄N₂O₃S [M + H] 445.1580; found 445.1574.

OCH₂CH₃), 3.29–3.37 (m, 1 H, OCHHCH₃), 3.52–3.59 (m, 1 H,

2

OCHHCH₃), 3.84–3.87 (m, 4 H, CHH and OCH₃), 4.04 (d, J =

3

15.2 Hz, 1 H, CHH), 5.13 (s, 1 H, CH), 6.94 (d, J = 8.8 Hz, 2 H,

3

ArH), 7.19 (d, J = 8.0 Hz, 2 H, ArH), 7.35 (d, J = 8.8 Hz, 2 H,

ArH), 7.38–7.42 (m, 2 H, ArH), 7.46–7.49 (m, 3 H, ArH), 8.16–

8.18 (m, 2 H, ArH), 10.99 (br. s, 1 H, NH) ppm. ¹³C NMR

(100 MHz, CDCl₃): δ = 15.2 (OCH₂CH₃), 42.5 (CH₂), 55.3

(OCH₃), 64.3 (OCH₂CH₃), 77.2 (CH), 114.3 (ArC), 125.7 (ArC),

126.6 (ArC), 127.6 (Csp²), 127.7 (ArC), 128.1 (ArC), 129.3 (ArC),

130.7 (ArC), 131.7 (ArC), 132.0 (ArC), 133.6 (Csp²), 134.2 (ArC),

138.5 (ArC), 160.3 (ArC), 169.4 (Csp²), 176.6 (CO) ppm. HRMS

(ESI): m/z calcd. for C₂₇H₂₅⁷⁹BrN₂O₃S [M + H] 536.0770; found

536.0768.

N-{5-[(4-Bromophenyl)(methoxy)methyl]-6-phenyl-4H-1,3-thiazin-2-

yl}benzamide (10cf): Yield 0.15 g (60%); yellow oil. IR (KBr): ν

˜

max

= 1681 (C=O), 3167 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

1.21 (t, ³J = 7.2 Hz, 3 H, OCH₂CH₃), 3.29–3.37 (m, 1 H,

OCHHCH₃), 3.52–3.60 (m, 1 H, OCHHCH₃), 3.86 (d, ²J =

N-{5-[Methoxy(phenyl)methyl]-6-(4-methoxyphenyl)-4H-1,3-thiazin-

2

15.6 Hz, 1 H, CHH), 4.05 (d, J = 15.2 Hz, 1 H, CHH), 5.10 (s, 1

2-yl}benzamide (10ag): Yield 0.13 g (58%); yellow solid; m.p. 55–

H, CH), 7.19 (d, ³J = 8.0 Hz, 2 H, ArH), 7.38–7.42 (m, 7 H, ArH),

7.46–7.48 (m, 3 H, ArH), 8.16–8.18 (m, 2 H, ArH), 10.96 (br. s, 1

H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 15.2 (OCH₂CH₃),

42.5 (CH₂), 64.3 (OCH₂CH₃), 77.1 (CH), 121.7 (ArC), 127.7 (ArC),

128.0 (ArC), 128.1 (Csp²), 128.9 (ArC), 129.3 (2ϫ ArC), 131.6

(ArC), 132.0 (ArC), 134.1 (Csp²), 134.6 (ArC), 136.2 (ArC), 138.4

(ArC), 168.8 (Csp²), 176.3 (CO) ppm. HRMS (ESI): m/z calcd. for

C₂₆H₂₃⁷⁹BrN₂O₂S [M + H] 506.0664; found 506.0665.

1

56 °C. IR (KBr): ν

= 1681 (C=O), 3195 (NH) cm^–1. H NMR

˜

max

(400 MHz, CDCl₃): δ = 3.32 (s, 3 H, OCH₃), 3.84 (s, 3 H, OCH₃),

3.88 (d, ²J = 15.2 Hz, 1 H, CHH), 4.08 (d, ²J = 15.2 Hz, 1 H,

3

CHH), 5.09 (s, 1 H, CH), 6.95 (d, J = 8.8 Hz, 2 H, ArH), 7.30–

3

4

7.32 (m, 3 H, ArH), 7.35–7.42 (m, 6 H, ArH), 7.48 (tt, J = 7.6, J

= 1.6 Hz, 1 H, ArH), 8.17–8.19 (m, 2 H, ArH), 11.03 (br. s, 1 H,

NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 42.5 (CH₂), 55.3

(OCH₃), 55.6 (OCH₃), 79.6 (CH), 114.3 (ArC), 126.0 (ArC), 126.7

(ArC), 127.6 (ArC), 127.8 (Csp²), 128.0 (ArC), 128.6 (ArC), 129.3

(ArC), 130.8 (ArC), 131.9 (ArC), 134.3 (Csp²), 136.4 (ArC), 139.0

(ArC), 160.3 (ArC), 169.7 (Csp²), 176.7 (CO) ppm. HRMS (ESI):

m/z calcd. for C₂₆H₂₄N₂O₃S [M + H] 445.1580; found 445.1574.

N-{5-[Methoxy(phenyl)methyl]-6-phenyl-4H-1,3-thiazin-2-

yl}benzamide (10cg): Yield 0.12 g (57%); yellow oil. IR (KBr): ν

˜

max

= 1680 (C=O), 3189 (NH) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =

2

3.33 (s, 3 H, OCH₃), 3.89 (d, J = 15.2 Hz, 1 H, CHH), 4.09 (d, J

= 15.6 Hz, 1 H, CHH), 5.07 (s, 1 H, CH), 7.28–7.32 (m, 3 H, ArH),

7.35–7.38 (m, 2 H, ArH), 7.40–7.51 (m, 8 H, ArH), 8.18–8.20 (m,

2 H, ArH), 11.01 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz,

CDCl₃): δ = 42.5 (CH₂), 56.6 (OCH₃), 79.5 (CH), 125.9 (ArC),

127.8 (ArC), 128.0 (ArC), 128.2 (Csp²), 128.9 (ArC), 129.2 (ArC),

129.3 (ArC), 129.4 (ArC), 131.9 (ArC), 134.2 (Csp²), 134.7 (ArC),

136.3 (ArC), 138.9 (ArC), 169.3 (Csp²), 176.5 (CO) ppm. HRMS

(ESI): m/z calcd. for C₂₅H₂₂N₂O₂S [M + H] 415.1475; found

415.1461.

N-{6-(4-Chlorophenyl)-5-[methoxy(phenyl)methyl]-4H-1,3-thiazin-2-

yl}benzamide (10bg): Yield 0.15 g (65 %); yellow solid; m.p. 55–

1

56 °C. IR (KBr): ν

= 1683 (C=O), 3196 (NH) cm^–1. H NMR

˜

max

(400 MHz, CDCl₃): δ = 3.32 (s, 3 H, OCH₃), 3.89 (d, ²J = 15.6 Hz,

1 H, CHH), 4.09 (d, J = 15.6 Hz, 1 H, CHH), 5.01 (s, 1 H, CH),

7.27–7.32 (m, 3 H, ArH), 7.35–7.44 (m, 8 H, ArH), 7.49 (tt, J =

7.2, J = 1.2 Hz, 1 H, ArH), 8.16–8.18 (m, 2 H, ArH), 10.94 (br. s,

2

3

4

1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 42.6 (CH₂), 56.7

(OCH₃), 79.7 (CH), 125.9 (ArC), 128.0 (Csp²), 128.1 (ArC), 128.7

(ArC), 129.0 (ArC), 129.2 (ArC), 129.3 (ArC), 130.8 (ArC), 132.0

(ArC), 133.2 (ArC and Csp²), 135.5 (ArC), 136.1 (ArC), 138.7

(ArC), 168.7 (Csp²), 176.4 (CO) ppm. HRMS (ESI): m/z calcd. for

C₂₅H₂₁³⁵ClN₂O₂S [M + H] 449.1085; found 449.1076.

2-(Isochroman-1-yl)-1-(4-methoxyphenyl)prop-2-en-1-one

(11ac):

1654

(C=O) cm^–1. H NMR (400 MHz, CDCl₃): δ = 2.85–3.00 (m, 2 H,

Yield 0.13 g (90%); yellowish oil. IR (KBr):

ν

˜

=

max

1

2

3

CH₂), 3.90 (s, 3 H, OCH₃), 3.93 (ddd, J_H,H= 11.3, J_H,H= 6.3,

2

3

²J_H,H= 4.9 Hz, 1 H, OCH₂), 4.17 (ddd, J_H,H= 11.3, J_H,H= 6.3,

²J_H,H= 4.9 Hz, 1 H, OCH₂), 5.71 (s, 1 H, =CH), 5.79 (s, 1 H,

N-{5-[(4-Bromophenyl)(ethoxy)methyl]-6-(4-chlorophenyl)-4H-1,3-

thiazin-2-yl}benzamide (10bf): Yield 0.15 g (57%); yellow solid; m.p.

3

=CH), 5.99 (s, 1 H, CHO), 6.97 (d, J_H,H= 8.9 Hz, 2 H, ArH),

7.04 (d, J_H,H= 7.0 Hz, 1 H, ArH), 7.17–7.22 (m, 3 H, ArH), 7.91

3

1

73–74 °C. IR (KBr): ν

= 1682 (C=O), 3188 (NH) cm^–1. H

˜

max

(d, ³J_H,H= 8.9 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃):

δ = 28.58 (CH₂), 55.44 (OCH₃), 62.13 (OCH₂), 74.84 (OCH),

113.53 (ArC), 125.83 (ArC), 126.01 (=CH₂), 126.53 (ArC), 126.70

(ArC), 128.88 (ArC), 130.00 (ArC), 132.11 (ArC), 134.12 (ArC),

135.19 (ArC), 148.81 (=C-C=O), 163.36 (ArC), 195.70 (C=O) ppm.

HRMS (ES): m/z calcd. for C₁₉H₁₈NaO₃[M + Na]⁺317.1148;

found 317.1149.

NMR (400 MHz, CDCl₃): δ = 1.22 (t, ³J = 7.2 Hz, 3 H,

OCH₂CH₃), 3.29–3.37 (m, 1 H, OCHHCH₃), 3.50–3.57 (m, 1 H,

OCHHCH₃), 3.87 (d, ²J = 15.6 Hz, 1 H, CHH), 4.05 (d, ²J =

3

15.6 Hz, 1 H, CHH), 5.05 (s, 1 H, CH), 7.16 (d, J = 8.0 Hz, 2 H,

ArH), 7.35–7.39 (m, 2 H, ArH), 7.41–7.43 (m, 3 H, ArH), 7.46–

7.49 (m, 3 H, ArH), 7.51–7.56 (m, 1 H, ArH), 8.14–8.17 (m, 2 H,

ArH), 10.88 (br. s, 1 H, NH) ppm. ¹³C NMR (100 MHz, CDCl₃):

δ = 15.2 (OCH₂CH₃), 42.7 (CH₂), 64.5 (OCH₂CH₃), 77.3 (CH),

2-(Isochroman-1-yl)-1-phenylprop-2-en-1-one (11bc): Yield 0.11 g

121.9 (ArC), 125.8 (ArC), 127.7 (ArC), 128.1 (ArC), 128.9 (Csp²), (83%); yellowish oil. IR (KBr): ν_max= 1660 (C=O) cm^–1. ¹H NMR

˜

2

129.3 (2 ϫ ArC), 129.7 (ArC), 130.7 (ArC), 131.8 (ArC), 132.1 (400 MHz, CDCl₃): δ = 2.87–2.95 (m, 2 H, CH₂), 3.95 (ddd, J_H,H

3

2

(ArC), 133.1 (Csp²), 135.6 (ArC), 138.2 (ArC), 168.3 (Csp²), 176.3 = 11.4, J_H,H= 6.8, J_H,H= 4.7 Hz, 1 H, OCH₂), 4.18 (ddd, J_H,H

7112

www.eurjoc.org

Eur. J. Org. Chem. 2015, 7091–7113

Electrophile-Mediated Reactions of Propargylic Derivatives

3

2

M. Ganschow, M. W. Hussong, M. Rudolph, F. Rominger,

A. S. K. Hashmi, Adv. Synth. Catal. 2014, 356, 680; d) L.-J.

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= 11.4, J_H,H= 6.8, J_H,H= 4.7 Hz, 1 H, OCH₂), 5.81 (s, 1 H,

3

=CH), 5.88 (s, 1 H, =CH), 6.03 (s, 1 H, CHO), 7.03 (d, J_H,H

7.0 Hz, 1 H, ArH), 7.16–7.24 (m, 3 H, ArH), 7.46–7.50 (m, 2 H,

ArH), 7.57–7.61 (m, 1 H, ArH), 7.86–7.88 (m, 2 H, ArH) ppm. ¹³

NMR (100 MHz, CDCl₃): δ = 28.61 (CH₂), 62.27 (OCH₂), 74.45

(OCH), 125.91 (ArC), 126.43 (ArC), 126.75 (ArC), 127.97 (=CH₂),

128.28 (ArC), 128.92 (ArC), 129.67 (ArC), 132.56 (ArC), 134.17

(ArC), 135.27 (ArC), 137.46 (ArC), 148.82 (=C-C=O), 196.96

(C=O) ppm. HRMS (ES): m/z calcd. for C₁₈H₁₆NaO₂[M + Na]⁺

287.1043l; found 287.1045.

=

C

Supporting Information (see footnote on the first page of this arti-

cle): Experimental details for the preparation of the starting materi-

als, the results of optimization studies, and copies of ¹H and ¹³C

NMR spectra.

[3] For representive publications on electrophile-mediated reac-

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Xin, B. Wan, Tetrahedron Lett. 2015, 56, 32; g) Y. Hu, R. Yi,

C. Wang, X. Xin, X. Wu, B. Wan, J. Org. Chem. 2014, 79,

3052; h) F. Yang, T. Jin, M. Bao, Y. Yamamoto, Tetrahedron

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Acknowledgments

The research was funded by the Research Council of Lithuania

(grant number MIP-15016).

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Received: August 17, 2015

Published Online: October 12, 2015

Eur. J. Org. Chem. 2015, 7091–7113

www.eurjoc.org

7113

Article Doi

Electrophile-Mediated Reactions of Functionalized Propargylic Substrates

DOI: 10.1002/ejoc.201501063

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Full text of DOI:10.1002/ejoc.201501063

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