Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of β-Substituted Vinylsulfones Using O- And S-Centered Nucleophiles

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Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of

β‑Substituted Vinylsulfones Using O- and S‑Centered Nucleophiles

Ashish Kumar Sahoo, Anjali Dahiya, Bubul Das, Ahalya Behera, and Bhisma K. Patel*

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ABSTRACT: An inimitable illustration of a green-light-induced,

regioselective difunctionalization of terminal alkynes has been

disclosed using sodium arylsulﬁnates and carboxylic acids in the

presence of eosin Y as the photocatalyst. The present methodology

is further demonstrated by employing NH₄SCN as an S-centered

nucleophile instead of carboxylic acid. The mechanistic inves-

tigation reveals a radical-induced iodosulfonylation followed by a

base-mediated nucleophilic substitution. The mechanism is

supported by various studies, viz., radical-trapping experiment,

ﬂuorescence quenching, and CV studies. In this protocol, (Z)-β-

substituted vinylsulfones are obtained, exclusively covering a broad range of alkynes and nucleophiles, which are often unaddressed.

The present strategy can tolerate structurally discrete substrates with steric bulk and diﬀerent electronic properties, which provides a

straightforward and practical pathway for the synthesis of highly functionalized (Z)-β-substituted vinylsulfones. Herein, C−O and

C−S bonds are assembled simultaneously with the concomitant introduction of important functional groups, viz., ester, thiocyanate,

and sulfone.

atom abstraction, causing serious problems in developing

radical-based alkyne difunctionalization.⁶

INTRODUCTION

■

Alkynes are well-established building blocks in organic synthesis,

which are useful due to their eﬃcient transformation into other

functionalities.¹In recent years, direct difunctionalization of

alkynes has grabbed the attention of chemists, in which

simultaneous introduction of two functional groups provides

either a tri- or a tetra-substituted alkene depending on whether

the alkene is terminal or internal.²Alkenes having multiple

substituents are prevalent in many bioactive molecules, natural

products, and pharmaceuticals, viz., tamoxifen, doxepin, etc.

Hence, the development of a newer methodology for their

synthesis is still in demand, and chemists always dreamed of

developing eﬃcient and suitable methods for their synthesis.³

Multicomponent reactions (MCRs) are popular because they

allow the construction of multifaceted structures starting from

simple substrates. In this context, MCR has been recognized as a

transformative tool, which not only increases eﬃciency and

productivity but also reduces the cost and environmental

impact.⁴Unlike alkenes, the application of MCRs to the

difunctionalization of alkynes is not well explored. Moreover,

alternative approaches require the use of organometallic species

and multistep transformations. Therefore, it is desirable to

develop a general, eﬃcient, and practical method for the

difunctionalization of terminal alkynes.⁵Mechanistically, a

general reaction pathway is speculated, in which the reaction

proceeds via the radical addition to an alkyne to form a vinylic

radical, which is then coupled with another radical partner to

form a substituted alkene. Generally, the vinyl radical is much

more reactive, so it is prone to hydrofunctionalization via H

However, difunctionalization can be achieved under a

condition that suppresses the H-abstraction capturing the

other radical partners.⁷Due to the high reactivity of radicals,

they are not always as selective as initially designed.^8a,bDue to

the importance of (Z)-alkenes, there are well-established

methods for their synthesis, viz., Wittig reaction,^8ccatalytic

alkynes hydrogenation,^8dand Negishi coupling.^8eNormally, a

transition metal is essential to attain selectivity in the

difunctionlization protocol. Hence, the synthetic approach to

(Z)-alkenes via a radical addition under a transition metal-free

condition is very intriguing.⁹

Nowadays, sulfonylation has gained a unique reputation as the

sulfur-containing compounds have remarkable biological

activity, pharmaceutical importance, and synthetic utility. For

instance, K11777 (I) is a well-known cysteine protease inhibitor,

and sulfone (II) is a Nrf activator, which has the potential for

curing Parkinson’s disease. There is a class of anti-HIV reverse

transcriptase inhibitors (III) having both indole moiety and

sulfonyl group (Figure 1).¹⁰Vinyl sulfones are utilized as

Received: June 8, 2021

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A

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Scheme 1. Difunctionalization of Terminal Alkynes

Figure 1. Bioactive compounds containing vinyl sulfones and a

thiocyanate group.

temperature. To our delight, a new product containing an ester

and a tosyl moiety was isolated in a 30% yield. The spectroscopic

analysis (¹H and ¹³C{¹H} NMR) revealed the structure of the

product to be (Z)-β-carboxy vinylsulfone (1bb′). Further, the

X-ray crystallography of one of its derivatives (1db′)

reconﬁrmed its structure and the (Z)-geometry (Figure 2,

Supporting Information). Although phenylacetylene (1) got

fully consumed, the formation of β-keto sulfone, β-iodo alkenyl

sulfone and a minor amount of phenylacetylene dimer as the side

products reduced the yield of the desired product (1bb′).

Inspired by this metal-free protocol, further operational

parameters were screened to maximize the product yield. For

this, phenylacetylene (1), sodium p-tolylsulﬁnate (b′), and p-

toluic acid (b) were chosen as the reacting components. Initially,

various inorganic bases were screened, and K₂CO₃was found to

be optimal compared to other bases such as Na₂CO₃(25%),

Cs₂CO₃(20%), KOH (15%), and NaOH (18%) (Table 1,

entries 2−5). The reaction was extremely sluggish in the absence

of base, and the product (1bb′) was isolated in a suppressed

yield (<10%) (Table 1, entry 6). This suggests that the base is

indispensable for the present difunctionalization protocol. The

use of fewer than 2 equiv of the base resulted in poor conversion,

but an excess amount of base led to the formation of β-keto

sulfone as the side product via a hydrolytic path. Next, diﬀerent

solvents were tested to enhance the product yield. The use of

CH₃CN instead of MeOH gave a 25% yield (Table 1, entry 7),

whereas DMSO (12%) and DMF (15%), gave a comparatively

lesser yield of the product (1bb′) (Table 1, entries 8 and 9).

Interestingly, an improved yield of 40% was obtained when

protic solvent such as EtOH was used (Table 1, entry 10).

Switching the catalytic system from eosin Y to Rose Bengal and

transition metal complex [Ru(bpy)₃]PF₆, failed to improve the

product yield beyond 25% (Table 1, entry 11 and 12).

Therefore, further optimizations were carried out using eosin

Y. Other iodine-based reagents were also tested in the hope of

getting a satisfactory yield. The use of KI (20%) and TBAI

(35%) as oxidants gave a lower yield of the product (Table 1,

entries 13 and 14). “When K₂S₂O₈was used no product

formation was observed which conﬁrms the role of iodine as an

iodinating agent.” (Table 1, entry 15). To further improve the

yield, the loadings of eosin Y and iodine were varied. At 3 mol %

eosin Y loading, 70% yield of the desired product was obtained

(Table 1, entry 16). Whereas, further increment (4 mol %) led to

no signiﬁcant change in the yield of the product (Table 1, entry

expedient synthons in many reactions. Besides this, sulfones are

good leaving groups that often show unique chemical

reactivity.¹¹Thus, a variety of organic transformations are

possible using the sulfonyl group, so aptly described as a

chemical chameleon by Trost.^11cIn this context, the develop-

ment of a newer methodology for the synthesis of such

molecules is deemed worthy of investigation.¹²

Recently, visible-light mediated functionalizations have

emerged as a signiﬁcant tool in contemporary organic chemistry.

Much of the potential of visible-light photoredox catalysis focus

on its ability to accomplish exotic bond formations that are not

possible using conventional approaches. However, most organic

compounds do not absorb visible light eﬃciently, which has

limited the application of photochemical synthesis. Therefore,

photocatalysts, usually transition-metal complexes of Ir, Ru, and

organic dyes, are often utilized to sensitize organic mole-

cules.^13,14The employment of organic dyes such as Rose Bengal,

eosin Y, and eosin B as photocatalysts has proven to be a

practical, greener, and better alternative due to their low cost,

less toxicity and at times superior reactivity compared to

transition metal-based photoredox catalysts. In particular, eosin

Y is used as a photoredox catalyst in several radical-based organic

transformations.¹⁴

In 2017, Nevado et al. reported a method for the

carbosulfonylation of alkynes via a multicomponent approach

giving trisubstituted alkenes (Scheme 1a).¹⁵In 2018, Han et al.

demonstrated an elegant visible light-mediated chlorosulfony-

lation of alkynes in the presence of the fac-Ir(bpy)₃photoredox

catalyst (Scheme 1b).¹⁶This method has certain merits over

existing reports such as the use of inexpensive organic dye as a

photocatalyst, one-pot strategy, and broad substrate scope due

to in situ replacement of halo group with appropriate

nucleophiles. Usually, transition metal catalysts are required

for the difunctionalization of alkynes, but herein, the visible

light-mediated, metal-free, multicomponent approach is articu-

lated for difunctionalization of terminal alkynes (Scheme 1c).

RESULTS AND DISCUSSION

■

To synchronize our assumption, we initiated a reaction between

phenylacetylene (1, 1 equiv), sodium p-tolylsulﬁnate (b′, 1

equiv), and p-toluic acid (b, 1.5 equiv) in the presence of K₂CO₃

(2 equiv), I₂(1 equiv), eosin Y (3 mol %), in methanol (2 mL)

under the irradiation of 20 W (2 × 10) green LEDs at room

B

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produce β-keto sulfone product.^6,7eThe surrounding reaction

temperature was maintained to room temperature (∼28 °C), by

using a fan near the reaction ﬂask thereby conﬁrming the

photochemical nature of this protocol (Figure 1, Supporting

Information).

a

Table 1. Optimization of the Reaction Conditions

With the optimized condition in hand, this protocol was

subsequently applied for the difunctionalization of various

substituted phenyl acetylenes using substituted benzoic acids

and sodium p-tolylsulﬁnate as the reacting partners. At ﬁrst, the

scope of diﬀerent benzoic acids (a−u) was tested with

phenylacetylene (1) and sodium p-tolyl sulﬁnate (b′) (Scheme

2). As can be seen from Scheme 2, a range of substituted benzoic

acids bearing electron-donating as well as electron-withdrawing

groups reacted smoothly with 1 and b′ to aﬀord the desired

difunctionalized products (1ab′−1ub′) in moderate yields

(Scheme 2). Benzoic acid (a) and its derivatives bearing

electron-donating substituents, such as p-Me (b) and p-OMe

(c), reacted smoothly and aﬀorded their corresponding

products (1ab′, 68%; 1bb′, 70%; 1cb′, 74%). The reaction

also worked eﬀectively with benzoic acids bearing electron-

withdrawing substituents, such as p-Cl (d) and p-Br (e), and

aﬀorded their desired products (1db′, 62%; 1eb′, 64%) but in

inferior yields compared to substrates having electron-donating

substituents. This may be due to the enhanced nucleophilicity of

substituted benzoic acids, which is driven by the +I and +R eﬀect

of the electron-donating groups. The use of o-substituted

benzoic acids, viz., o-Br (f) and o-I (g), aﬀorded their

corresponding (Z)-β-carboxy vinylsulfones (1fb′, 65%; 1gb′,

63%) (Scheme 2).

Apart from the monosubstituted carboxylic acids, di- and

trisubstituted benzoic acids (h−j) were also employed, and the

desired products (1hb′, 62%; 1ib′, 64%; 1jb′, 52%) were

isolated in moderate yields. The aliphatic carboxylic acids such

as acetic acid (k), pivalic acid (l), hexanoic acid (m), and

saturated fatty acids such as octanoic acid (n), capric acid (o),

and stearic acid (p) all reacted eﬃciently, giving their (Z)-β-

carboxy vinylsulfones (1kb′, 1lb′, 1mb′, 1nb′, 1ob′, and 1pb′)

in 65%, 70%, 68%, 72%, 75%, and 65% yields, respectively

(Scheme 2). Similarly, cyclopropylacetic acid (q) and 1-

admantanecarboxylic acid (r) gave their expected (Z)-β-carboxy

vinylsulfones 1qb′ (64%) and 1rb′ (58%). Moderate yields of

the products 1sb′ (60%), 1tb′, 62%), and 1ub′ (55%) were

obtained when polyaromatic carboxylic acids, viz., piperonylic

acid (s), 2-napthanoic acid (t), and heteroaromatic acid such as

thiophene 2-carboxylic acid (u), were reacted under the

optimized conditions.

Next, the scope of this methodology was extended by reacting

a variety of terminal alkynes (2−11) with p-toluic acid (b) and

sodium p-tolylsulﬁnate (b′), and the results are summarized in

Scheme 3. Phenyl acetylenes bearing electron-donating and

electron-withdrawing substituents in the phenyl ring (2−11)

underwent an eﬃcient reaction with p-toluic acid (b) and

sodium p-tolylsulﬁnate (b′), giving their respective (Z)-β-

carboxy vinylsulfones (2bb′−11bb′) in good to moderate yields

(61−78%). Phenyl acetylenes bearing electron-donating sub-

stituents such as p-Me (2), p-OMe (3), p-^tBu (4), and m-Me (5)

aﬀorded their corresponding products 2bb′ (74%), 3bb′ (78%),

4bb′ (75%), and 5bb′ (70%) in moderate yields. Next, a series

of phenyl acetylenes bearing electron-withdrawing substituents

such as p-Cl (6), p-Br (7), p-F (8), m-F (9), and m-Cl (10) were

reacted, and all gave their anticipated products 6bb′ (68%),

7bb′ (70%), 8bb′ (64%), 9bb′ (61%), and 10bb′ (65%) in

acceptable yields. A moderate yield of the product 11bb′ (71%)

b

photocatalyst

(mol %)

oxidant

(equiv)

yield

entry

base (equiv)

K₂CO₃(2)

solvent

(%)

1

2

3

4

5

6

7

8

eosin Y (2)

I₂(1)

Na₂CO₃(2) I₂(1)

MeOH

CH₃CN

DMSO

DMF

30

25

20

15

18

<10

25

12

15

40

25

20

Cs₂CO₃(2)

KOH (2)

NaOH (2)

I₂(1)

K₂CO₃(2)

9

10

11

12

EtOH

Rose Bengal (2) K₂CO₃(2)

[Ru(bpy)₃]

PF₆(2)

K₂CO₃(2)

13

14

15

16

17

18

19

20

21

22

23

eosin Y (2)

eosin Y (3)

eosin Y (4)

eosin Y (3)

K₂CO₃(2)

KI (1)

TBAI (1)

K₂S₂O₈(1) EtOH

I₂(1)

I₂(0.5)

I₂(1.5)

I₂(1)

EtOH

20

35

nd

c

EtOH

70

72

45

69

35

30

d

e

nd

eosin Y (3)

a

Reaction conditions: 1 (0.15 mmol), b (1.5 equiv), b′ (1 equiv),

catalyst (mol %), base (equiv), and oxidant (equiv) in 2 mL solvent

b

with a 2 × 10 W green LEDs irradiation at room temperature. Yield

of isolated product. nd = not detected. Reaction performed using 10

W (430 nm) blue LEDs light. Reaction performed using 10 W white

c

d

e

LEDs light.

17). A satisfactory yield was obtained using 1 equiv of iodine

(Table 1, entry 18, and 19). Since the iodine is serving as an

iodinating agent, so the use of less than one equivalent of iodine

led to poor conversion and a higher amount (1.5 equiv) was not

beneﬁcial. The wavelength and intensity of the visible light can

aﬀect the rate of photochemical reactions. Thus, the reaction

was carried out using (2 × 10 W) blue LEDs (430 nm) and (2 ×

10 W) white LEDs (Table 1, entries 20 and 21). As can be seen,

previously used (2 × 10 W) green LEDs (513 nm) provided

superior result (Table 1, entry 16). The intensity of the blue light

is indeed higher than the green light. The excitation maxima of

eosin Y in a basic ethanolic solution was measured and found to

be 542 nm, which perfectly overlaps in the green region (490−

570 nm) and the green LED used had a wavelength of 513 nm.

Thus, the green light is a better choice for the excitation of eosin

Y which also minimalizes the formation of side products by

avoiding the decomposition of iodine compared to LEDs of

lower wavelength (higher energy). Control experiments suggest

that both the catalyst and iodine are essential for this reaction

(Table 1, entries 22 and 23). The eosin Y is indispensable for this

reaction as it suppresses the other competing paths such as

hydrofunctionalizationand reaction with molecular oxygen to

C

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a b

,

Scheme 2. Scope of (Z)-β-Carboxy Vinylsulfones with Diﬀerent Acids

a

Reaction conditions: 1 (0.5 mmol), a−u (0.75 mmol), b′ (0.5 mmol), I₂(0.5 mmol), K₂CO₃(1 mmol), eosin Y (3 mol %) in 2 mL of ethanol, 2

b

c

× 10 W green LEDs. Isolated yield. Ten mmol scale.

was obtained when cyclohexyl acetylene was reacted under the

optimized condition (Scheme 3). After successfully synthesizing

a library of (Z)-β-carboxy vinylsulfones using terminal alkynes,

we were curious to know the fate of the reaction with an internal

alkyne (12). Unlike terminal alkynes, the internal alkyne

provided β-iodo sulfone (12b′, 80%) under the present

photochemical condition.

The generality of this method was further extended to various

sodium arylsulﬁnates (a′, c′−i′) with terminal alkynes (1, 2, 4,

7) and carboxylic acids {p-Me (b), p-OMe (c), p-Cl (d)} having

diﬀerent electronic eﬀects. The electronically neutral sodium

benzenesulﬁnate (a′) gave the anticipated (Z)-β-carboxy

vinylsulfones 2ba′ (70%), 4ba′ (72%), and 7ba′ (68%) in

good yields. The reaction also worked eﬀectively with sodium 4-

(tert-butyl)benzenesulﬁnate (c′) and provided the anticipated

product (1bc′) in 74% yield. Similarly, sodium arylsulﬁnates

having moderately electron-withdrawing substituents {p-Cl

(d′), p-Br (e′)} underwent eﬃcient reactions with phenyl-

acetylene (1) and carboxylic acids {p-Me (b), p-OMe (c), p-Cl

(d)}, resulting in the corresponding products 1bd′ (66%), 1be′

(67%), 1ce′ (73%), and 1de′ (62%) in good yields (Scheme 4).

Next, sodium arylsulﬁnates bearing strong electron-withdrawing

substituents such as p-NO₂(f′) and 2-Br-4CF₃(g′) were tested,

and the corresponding (Z)-β-carboxy vinylsulfones 1bf′ (58%)

and 1bg′ (50%) were obtained in acceptable yields. Apart from

aryl substituents, both heteroaryl (h′) and sodium alkylsulﬁnate

(i′) successfully yielded their anticipated products 1bh′ (52%)

and 1bi′ (70%) under present conditions. Organic thiocyanates

(RSCN) are potential synthetic intermediates, as the sulfur-

containing compounds have remarkable bioactivity and

synthetic utility.^10eThus, under the established reaction

condition for carboxylic acid, NH₄SCN (v) was tested as a S-

centered nucleophile to further expand the utility of the present

protocol. Gratifyingly, −SCN was successfully employed, and its

difunctionalized products 2vb′, 4vb′, and 5va′ were obtained in

55%, 58%, and 54% yields, respectively (Scheme 4).

To study the electronic eﬀect of the substituents present on

the phenylacetylene and benzoic acid, a few intermolecular

D

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a b

,

Scheme 3. Scope of (Z)-β-Carboxy Vinylsulfones with Diﬀerent Alkynes

a

Reaction conditions: 2−12 (0.5 mmol), b (0.75 mmol), b′ (0.5 mmol), I₂(0.5 mmol), K₂CO₃(1 mmol), eosin Y (3 mol %), ethanol (2 mL) in 2

b

c

× 10 W green LEDs. Isolated yield. Under unoptimized conditions.

competitive reactions were carried out. In our ﬁrst experiment,

an equimolar mixture of p-toluic acid (b) and p-chlorobenzoic

acid (d) was reacted with phenylacetylene (1) and sodium p-

tolylsulﬁnate (b′). The yields of the p-Me (b)-substituted

product (1bb′, 30%) was higher than the p-Cl (d) product

(1db′, 22%), which is evident from the yield pattern obtained in

Scheme 2. The higher electron density at the carboxylate anion

for substrate b, having an electron-donating group (due to + I

eﬀect), makes it a better nucleophile thus, giving a higher yield of

the product {Scheme 5 (i)}. In the second experiment, an

equimolar mixture of 4-ethynyltoluene (2) and 1-chloro-4-

ethynylbenzene (6) was reacted with p-toluic acid (b) and

sodium p-tolylsulﬁnate (b′) under the standard conditions. It

was observed that phenylacetylene, having an EDG, shows

better reactivity {Scheme 5 (ii)}, which is also in agreement with

the yield pattern found in Scheme 3. 4-Ethynltoluene (2)

provided higher yields of the product, which is due to the better

stabilization of the intermediate vinyl radical formed.

To understand the mechanism of this transformation,

systematic investigations were carried out based on some

literature precedents.¹⁷To validate the radical nature of the

reaction, two independent reactions were performed, one in the

presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 2

equiv) and the other with 2,6-ditertbutyl-4-methyl phenol

(BHT, 2 equiv). In the case of TEMPO, no product was

observed, while BHT provided a < 10% yield of the product

(1bb′), thereby suggesting the radical nature of the reaction

{Scheme 6 (i)}. The BHT adduct (M) with sodium p-

tolylsulﬁnate (b′) was obtained in 65% yield, which was further

characterized by NMR and HRMS analysis. The iodo

intermediate (B) was identiﬁed by the HRMS analysis of the

reaction mixture. In a control experiment, the reaction of 1-((2-

iodo-2-phenylvinyl)sulfonyl)-4-methylbenzene (B) with p-

toluic acid (b)/K₂CO₃{Scheme 6 (ii)} both in the presence

and absence of light yielded the identical product 1bb′.

However, a slight reduction (12%) in the yield was observed

in the absence of light, thereby suggesting a positive inﬂuence of

light for this addition−elimination step, which is possibly due to

the facile cleavage of the C−I bond in the presence of light.¹⁷

To further conﬁrm the radical nature of this protocol, the

Stern−Volmer ﬂuorescence quenching experiment of eosin Y

was performed using sodium p-toluene sulﬁnate (b′) as the

quencher. Initially, the excitation and emission spectra of eosin Y

were examined, and a ﬂuorescence maximum was obtained at

534 nm when excited at 515 nm (excitation maximum of eosin

Y, see Supporting Information). The peak at 534 nm gradually

decreases upon increasing the quencher concentration (5−35

mM) (Figure 2a). Similarly, a Stern−Volmer ﬂuorescence

quenching experiment was carried out using in situ generated

RSO₂I obtained by mixing and stirring RSO₂Na and I₂for 2 h. A

better quenching pattern of the eosin Y was observed in the

latter case, which suggests more facile electron transfer between

the catalyst and the quencher RSO₂I as compared to that of

RSO₂Na (Figure 2b). With these data, the Stern−Volmer graph

for both experiments was plotted using the equation I₀/I_t= 1 +

K

_SV[Q], where I₀and I_tare the integrated emission intensity in

the absence and presence of quencher and K_svis the quenching

constant. A linear quenching was observed in both cases (Figure

2c,d).

E

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a b

,

Scheme 4. Scope of (Z)-β-Carboxy Vinylsulfones with Diﬀerent Sodium Aryl Sulﬁnates

a

Reaction conditions: 1−7 (0.5 mmol), b−d, v (0.75 mmol), a′, c′−i′ (0.5 mmol), I₂(0.5 mmol), K₂CO₃(1 mmol), eosin Y (3 mol %), ethanol (2

b

c

mL) in 2 × 10 W green LEDs. Isolated yield. Under unoptimized conditions.

Scheme 5. Intermolecular Competition Experiments

These observations were further supported by redox potential

values of the eosin Y and a mixture of sodium p-toluene sulﬁnate

and iodine. The observed E_{1/2 red}value of the RSO₂I species

(RSO₂Na + I₂) was found to be −0.376 V vs SCE (−0.42 V vs

A closer look at the CV graph of RSO₂I shows a small anodic

peak at 0.357 V and a cathodic peak at 0.457 V, which closely

resembles the literature value of NaI (Figure 3a).^18bThis

conﬁrms that the formation of sulfonyl iodide was completed

before the electric input started. For a better understanding, the

CV experiment of RSO₂Na was also recorded (Figure 3b). The

Ag/AgCl sat. KCl), which is greater than the E_{1/2 oxd}value of EY^•

̅

(−1.06 V vs SCE) (for details, see Supporting Information).^18a

F

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Scheme 6. Control Experiments

Figure 2. Stern−Volmer quenching experiments (see Supporting Information).

observed E_{1/2 red}value of RSO₂Na species was found to be

−1.006 V vs SCE (−1.05 V vs Ag/AgCl sat. KCl), whereas, for

the RSO₂I species (RSO₂Na + I₂), the E_{1/2 red}value was found at

−0.376 V vs SCE (−0.42 V vs Ag/AgCl sat. KCl). Therefore, the

species RSO₂I have a higher tendency to gain an electron from

the EY radical anion compared to the RSO₂Na.

On the basis of the above experiments and previous reports, a

plausible mechanism has been proposed in Scheme 7.¹⁹In the

presence of green LEDs, eosin Y (EY) is ﬁrst photoexcited,

which is reductively quenched by an iodide ion.^19a−dThe

reaction of sodium sulﬁnate and iodine generates sulfonyl

iodide, which is reduced by an EY anion radical to give a sulfonyl

radical.^19e−gNext, the addition of a sulfonyl radical to the

terminal alkyne (1) gives a vinyl sulfone radical intermediate

(A). The formation of a vinyl carbocation via the SET process

and the subsequent attack of carboxylate is completely ruled out,

as this reaction does not proceed in the absence of iodine. The

radical addition of iodine to intermediate (A) generates a β-iodo

sulfone intermediate (B) (detected by HRMS analysis).

Subsequently, a base-promoted nucleophilic attack of the

carboxylate ion provides an intermediate (C), which is followed

by an addition−elimination process to give the corresponding

(Z)-1-phenyl-2-tosylvinyl benzoate (1ab′) (Scheme 7).

Next, (Z)-1-phenyl-2-tosylvinyl 4-methylbenzoate (1bb′)

was subjected to a few useful organic transformations as

shown in Scheme 8. Acid hydrolysis of (Z)-1-phenyl-2-

tosylvinyl 4-methylbenzoate (1bb′) furnished 1-phenyl-2-

tosylethan-1-one (X) in 80% isolated yield. Treatment of (Z)-

1-phenyl-2-tosylvinyl 4-methylbenzoate (1bb′) with butylamine

resulted in the formation of 1-phenyl-2-tosylethan-1-one (X)

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Figure 3. Cyclic voltammetry experiments (see Supporting Information).

Scheme 7. Plausible Mechanism for the Synthesis of (Z)-β-

Carboxy Vinylsulfones

multicomponent approach, covering a wide range of substrate

scope. In this protocol, C−O and C−S bonds are constructed

simultaneously with the introduction of important functional

groups such as ester, thiocyanate, and sulfone.

EXPERIMENTAL SECTION

■

General Information. Starting materials (acetylenes and carbox-

ylic acids) were commercially available (Sigma-Aldrich or Alfa-Aesar or

TCI chemicals) and used as received. Some aryl and alkyl sodium

sulﬁnates were commercially available (a′−d′), while others (e′−i′)

were prepared following the literature procedure.²¹The sodium

sulﬁnates obtained were used as such without further puriﬁcation.

Organic extracts were dried over anhydrous sodium sulfate. Solvents

were removed in a rotary evaporator under reduced pressure. Silica gel

(60−120 mesh size) was used for the column chromatography.

Reactions were monitored by TLC on silica gel 60 F₂₅₄(0.25 mm).

NMR spectra were recorded in CDCl₃as the internal standard for ¹H

NMR (400, 500, and 600 MHz) and ¹³C{¹H} NMR (100, 125, and 150

MHz). MS spectra were recorded using the ESI mode. IR spectra were

recorded in KBr or neat.

Light Information. Philips 10 W green LEDs (513 nm) were used

as a light source for this light-promoted reaction without any ﬁlter.

Borosilicate glass was used as the reaction vessel. The distance from the

light source to the irradiation vessel was approximately ∼6−8 cm. A

regular fan was used for proper aeration to maintain the temperature

28−30°C (Figure S1).

Scheme 8. Post-Synthetic Modiﬁcation

General Procedure for the Synthesis of (Z)-β-Carboxy

Vinylsulfone (1bb′). To an oven-dried 10 mL borosilicate vial were

added phenylacetylene (1) (0.5 mmol, 51.06 mg), sodium p-

tolylsulﬁnate (b′) (0.5 mmol, 89.09 mg), and p-toluic acid (b) (0.75

mmol, 102 mg), eosin Y (3 mol %, 9.7 mg), I₂(1 equiv, 126 mg), and

K₂CO₃(2 equiv, 138 mg). After that, 2 mL of EtOH was added, and the

reaction mixture was stirred at room temperature for 48 h, tentatively at

a distance of ∼6−8 cm from two 10 W green LED bulbs. After

completion of the reaction (monitored by TLC analysis), the solvent

was removed in vacuo, and the mixture was admixed with 25 mL of ethyl

acetate followed by washing with a saturated solution of aqueous

Na₂S₂O₃(1 × 10 mL) and aqueous NaHCO₃(1 × 10 mL). The organic

layer was dried over anhydrous Na₂SO₄, and the solvent was evaporated

under reduced pressure. The crude residue thus obtained was puriﬁed

by column chromatography over silica gel (60−120 mesh) using

hexane and ethyl acetate (9:1) as an eluent to aﬀord the (Z)-1-phenyl-

2-tosylvinyl 4-methylbenzoate (1bb′) in 70% yield. The identity and

purity of the product were conﬁrmed by spectroscopic analysis.

General Procedure for 10 mmol Scale Reaction of (Z)-1-

Phenyl-2-tosylvinyl 4 methylbenzoate (1bb′). To an oven-dried

50 mL borosilicate round-bottom ﬂask were added phenylacetylene (1)

(10 mmol, 1.021 g) sodium p-tolylsulﬁnate (b′) (10 mmol, 1.782 g),

and p-toluic acid (b) (15 mmol, 2.040 g), eosin Y (3 mol %, 0.194 g), I₂

(10 mmol, 2.520 g), and K₂CO₃(20 mmol, 2.760 g). After that, 30 mL

of EtOH was added, and the reaction mixture was stirred at room

temperature for 48 h, tentatively at a distance of ∼6−8 cm from two 10

and N-acylated product (Y). Thus, (Z)-1-phenyl-2-tosylvinyl 4-

methylbenzoate (1bb′) served as an eﬃcient acyl-transfer

reagent (Scheme 8). Though α-sulfonylated ketones can be

accessed via the method reported by Lan et al. using substituted

aryl ketones and sodium p-tolylsulﬁnate, this is yet another path

to α-sulfonylated ketones with the beneﬁt of concurrent N-

acylation at an ambient temperature.²⁰

CONCLUSION

■

In summary, an elegant visible-light-mediated method for the

difunctionalization of terminal alkynes is established using

sodium p-toluenesuﬁnate and O- and S-centered nucleophiles as

the reacting partners. This methodology allows the useful

synthesis of many valuable (Z)-β-substituted vinylsulfones via a

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W green LED bulbs. After completion of the reaction (monitored by

TLC analysis), the solvent was removed in vacuo, and the mixture was

admixed with 100 mL of ethyl acetate followed by washing with a

saturated solution of aqueous Na₂S₂O₃(1 × 30 mL) and aqueous

NaHCO₃(1 × 30 mL). The organic layer was dried over anhydrous

Na₂SO₄, and the solvent was evaporated under reduced pressure. The

crude residue thus obtained was puriﬁed by column chromatography

over silica gel (60−120 mesh) using hexane and ethyl acetate (9:1) as

an eluent to aﬀord the (Z)-1-phenyl-2-tosylvinyl 4-methylbenzoate

(1bb′) in 52% (2.04 g) yield. The identity and purity of the product

were conﬁrmed by spectroscopic analysis.

General Procedure for the Synthesis of 1-Phenyl-2-tosylethan-1-

one (X). To an oven-dried 5 mL round-bottom ﬂask were added (Z)-1-

phenyl-2-tosylvinyl 4-methylbenzoate (1bb′) (137 mg, 0.5 mmol) and

1 mL of 5 M HCl. The ﬂask was ﬁtted with a condenser, and the

reaction mixture was stirred in a preheated oil bath at 120°C for 4 h.

Next, the reaction mixture was cooled to room temperature and

admixed with ethyl acetate (20 mL). The organic layer was washed with

saturated sodium bicarbonate solution (2 × 5 mL) and dried over

Na₂SO₄, and the solvent was removed under reduced pressure. The

crude product so obtained was puriﬁed over a column of silica gel

(hexane/ethyl acetate, 17:3) to aﬀord the 1-phenyl-2-tosylethan-1-one

(110 mg, yield 80%) (X). The identity and purity of the product were

conﬁrmed by spectroscopic analysis.

General Procedure for the Synthesis of N-Butyl-4-methylbenza-

mide (Y). To an oven-dried 5 mL round-bottom ﬂask were added (Z)-

1-phenyl-2-tosylvinyl 4-methylbenzoate (1bb′) (137 mg, 0.5 mmol)

and BuNH₂(1.2 equiv). Next, 2 mL of DCM was added, and the

reaction mixture was stirred at room temperature for 24 h. After

completion of the reaction, the solvent was evaporated, and the reaction

mixture was admixed with ethyl acetate (20 mL). The organic layer was

washed with brine solution (2 × 5 mL) and dried over Na₂SO₄, and the

solvent was removed under reduced pressure. The crude product

obtained was puriﬁed over a column of silica gel to aﬀord 1-phenyl-2-

tosylethan-1-one (X, 55%) and N-butyl-4-methylbenzamide (Y, 55%).

The identity and purity of the product were conﬁrmed by spectroscopic

analysis.

emission was observed at 534 nm. For each ﬂuorescence quenching

experiment, a 10 μL (1 M) solution of sodium p-toluene sulﬁnate was

added to eosin Y solution (1 mM) taken in a ﬂuorescence cuvette, and

ﬂuorescence emission spectra were recorded after each addition (Figure

2b). As evident from Figure 2b, a decrease in emission intensity was

observed after each addition of sodium p-toluene sulﬁnate (5 → 35

mM). This conﬁrms the electron transfer between eosin Y and

quencher sodium p-toluene sulﬁnate (b′). A true ﬂuorescence

quenching phenomenon of eosin Y under various concentrations of

sodium p-toluene sulﬁnate was demonstrated from the Stern−Volmer

graph using the equation I₀/I_t= 1 + K_SV[Q], where I₀and I_tare

integrated emission intensity in the absence and presence of quencher

and Ksv is quenching constant. As evident from Figure 2c, a linear

quenching was observed, which conﬁrmed the electron transfer

between eosin Y and quencher sodium p-toluene sulﬁnate (b′).

CV Experiments Performed to Determine the Redox Potentials.

Cyclic voltammetry (CV) was performed using a three-electrode cell

conﬁguration comprising a platinum sphere, a platinum plate, and

Ag(s)/AgNO₃(0.01 M) as the working, auxiliary, and reference

electrodes, respectively. [Cyclic voltammetry experiment of RSO₂I

(RSO₂Na + I₂) taken at a scan rate 100mv/s. Experiment conditions:

init E = 2.0 V, high E = 2.0 V, low E = −2.0 V, init P/N = N, scan rate =

0.1 V/s, sample interval = 0.001 V, quiet time = 2s, sensitivity = 2e⁻⁴A/

V]. The supporting electrolyte used was tetraethylammonium

hexaﬂuorophosphate (TEAHFP) (C₂H₅)₄N(PF₆). Samples were

prepared with a substrate concentration of 0.01 M in a 0.1 M TEAHFP

in an acetonitrile electrolyte solution. From the result, it was found that

E_red= −1.06 V vs SCE, whereas E*_Oxd(RSO₂I) = −0.37 V vs SHE

(experimental value −0.42 V vs Ag/AgCl) (Figure 2d), which clearly

•

̅

indicated that the catalyst eosin Y (EY ) can easily donate an electron to

the RSO₂I species, which provides strong evidence to the catalytic cycle

suggested in mechanism (Scheme 7).

Spectral Data. (Z)-1-Phenyl-2-tosylvinyl Benzoate (1ab′):

Procedure for Radical Trapping Experiment. To prove the

photocatalytic radical pathway, a standard experiment between 1, b,

and b′ was carried out in the presence of TEMPO (2 equiv) and BHT

(2 equiv) under otherwise identical conditions. While in the former, no

formation of the desired product (1bb′, 0%) was observed, but the

latter radical scavenger provided <10% yield of 1bb′. In the case of BHT

as a scavenger, the tosyl radical was trapped, and the adduct (M) was

obtained in 65% yield, thereby conﬁrming the radical nature of the

present protocol (Schemes 6 and S1). The adduct (M) was puriﬁed by

column chromatography over silica gel (60−120 mesh) using hexane

and ethyl acetate (49:1) as an eluent to aﬀord the 2,6-di-tert-butyl-4-

(tosylmethyl)phenol (M) in 65% yield. The identity and purity of the

product were conﬁrmed by spectroscopic analysis (Scheme S1).

HRMS Study for the Detection of Reaction Intermediates. In

this study, compound 1bb′ was taken as a representative example, and a

standard experiment between 1, b, and b′ was carried out. After 2 h of

reaction, a small aliquot was withdrawn from the reaction mixture and

subjected to HRMS analysis after diluting it with CH₃CN/H₂O

(60:40). The formation of the 2-iodo-2-phenylvinyl)sulfonyl)-4-

methylbenzene (B) intermediate (Scheme 6) was judged from the

appearance of a peak at [M + H]⁺= 384.9751 (Scheme S2). To further

conﬁrm the intermediacy of B, a standard experiment was carried out

between presynthesized B and p-toluic acid (b) in the presence of

K₂CO₃(2 equiv) and ethanol (2 mL) in the dark at room temperature.

The desired product 1bb′ was obtained in 68% yield, thereby

suggesting the involvement of this intermediate in the present protocol

(Scheme S2).

white solid (130 mg, 68% yield); mp 120 −122 °C; puri ﬁ ed over a

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.13 (d, 2H, J = 7.2 Hz), 7.81 (d, 2H, J = 8.4 Hz), 7.68 (t, 1H, J

= 7.2 Hz), 7.54 (t, 2H, J = 7.8 Hz), 7.50 (d, 2H, J = 7.8 Hz), 7.43 (t, 1H,

J = 7.2 Hz), 7.36 (t, 2H, J = 7.8 Hz), 7.24 (d, 2H, J = 7.8 Hz), 6.81 (s,

1H), 2.39 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 163.4, 156.7,

144.7, 138.6, 134.4, 132.4, 131.8, 130.7, 129.9, 129.2, 128.9, 128.4,

128.1, 126.2, 118.7, 21.8; IR (KBr, cm⁻¹) 3061, 2925, 2857, 1744, 1616,

1453, 1234, 1061; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₂H₁₈O₄SNa [M + Na]⁺401.0818, found 401.0835.

(Z)-1-Phenyl-2-tosylvinyl 4-Methylbenzoate (1bb′):

brown solid (138 mg, 70% yield); mp 102 −104 °C; puri ﬁ ed over a

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 7.87 (d, 2H, J = 8.0 Hz), 7.66 (d, 2H, J = 8.0 Hz), 7.35 (t, 2H, J

= 7.2 Hz), 7.27 (d, 1H, J = 7.2 Hz), 7.17 −7.23 (m, 4H), 7.10 (t, 2H, J =

8.4 Hz), 6.66 (s, 1H), 2.33 (s, 3H), 2.25 (s, 3H); ¹³C{¹H} NMR

(CDCl₃, 100 MHz) δ 163.4, 156.9, 145.4, 144.6, 138.7, 132.5, 131.7,

130.8, 129.9, 129.6, 129.2, 128.1, 126.2, 125.7, 118.7, 22.0, 21.8; IR

(KBr, cm⁻¹) 3066, 2945, 2847, 1740, 1610, 1235, 1062; HRMS (ESI/

Q-TOF) (m /z ) calcd for C₂₃H₂₄O₄SN [M + NH₄]⁺410.1421, found

410.1420.

UV−Visible Spectroscopy and Fluorescence Quenching Experi-

ment (Stern−Volmer Studies). A 1 mM solution was prepared by

mixing eosin Y in water by an appropriate dilution of 0.01 M stock

solution and taken in a quartz UV cuvette of a 1 cm path length. The

UV−visible spectroscopy showed λ_maxof 515 nm (Figure 2a). For the

ﬂuorescence measurement, the sample was excited at 515 nm, and the

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(Z)-1-Phenyl-2-tosylvinyl 4-Methoxybenzoate (1cb′):

7.76 (dd, 1H, J₁= 7.6 Hz, J₂= 1.2 Hz), 7.57 (dd, 2H, J₁= 3.6 Hz, J₂= 7.2

Hz), 7.52 (dd, 1H, J₁= 7.2 Hz, J₂= 7.6 Hz), 7.49 (dd, 1H, J₁= 4.8 Hz, J₂

= 3.6 Hz), 7.46 (t, 1H, J = 4.0 Hz), 7.43 −7.45 (m, 1H), 7.40 (t, 2H, J =

7.6 Hz), 7.28 (d, 1H, J = 2.8 Hz), 6.77 (s, 1H), 2.41 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 100 MHz) δ 162.2, 156.2, 144.9, 138.4, 135.0, 134.0,

133.17, 132.19, 131.8, 130.0, 129.6, 129.2, 127.9, 127.7, 126.4, 123.0,

118.3, 21.8; IR (KBr, cm⁻¹) 3063, 2926, 2850, 1760, 1619, 1228, 1149,

1076; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₂H₂₁BrO₄SN [M +

NH₄]⁺474.0369, found 474.0367.

brown solid (152 mg, 74% yield); mp 130 −132 °C; puri ﬁ ed over a

(Z)-1-Phenyl-2-tosylvinyl 2-Iodobenzoate (1gb′):

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.07 (d, 2H, J = 9.2 Hz), 7.81 (d, 2H, J = 8.4 Hz), 7.49 (t, 2H, J

= 4.2 Hz), 7.42 (t, 1H, J = 7.2 Hz), 7.36, (t, 2H, J = 7.4 Hz), 7.23 (d, 2H,

J = 8.0 Hz), 7.00 (d, 2H, J = 8.8 Hz), 6.79 (s, 1H), 3.92, (s, 3H), 2.39 (s,

3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 164.6, 163.0, 157.0, 144.6,

138.7, 132.9, 132.6, 131.7, 129.9, 129.2, 128.1, 126.2, 120.7, 118.7,

114.2, 55.8, 21.8; IR (KBr, cm⁻¹) 3066, 2957, 2839, 1741, 1605, 1511,

1242, 1167, 1065; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₃H₂₁O₅S

[M + H]⁺409.1104, found 409.1103.

white solid (158 mg, 63% yield); mp 115 −117 °C; puri ﬁ ed over a

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 400

(Z)-1-Phenyl-2-tosylvinyl 4-Chlorobenzoate (1db′):

MHz) δ 8.21 (dd, 1H, J₁= 8.0 Hz, J₂= 1.6 Hz), 7.99 (d, 1H, J = 8.0 Hz),

7.71 (d, 2H, J = 8.4 Hz), 7.42 −7.45 (m, 3H), 7.34 (t, 1H, J = 7.2 Hz),

7.28 (t, 2H, J = 7.2 Hz), 7.15 (dd, 3H, J₁= 8.0 Hz, J₂= 6.4 Hz), 6.65 (s,

1H), 2.30 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 162.4, 156.2,

144.9, 142.2, 138.4, 134.1, 132.9, 132.2, 132.1, 131.8, 130.0, 129.2,

128.5, 128.0, 126.4, 118.4, 95.6, 21.9; IR (KBr, cm⁻¹) 3061, 2922, 2839,

1756, 1622, 1227, 1148, 1071; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₂H₁₈IO₄S [M + H]⁺504.9965, found 504.9957.

(Z)-1-Phenyl-2-tosylvinyl 4-Chloro-2-iodobenzoate (1hb′):

white solid (128 mg, 62% yield); mp 89 −91 °C; puri ﬁ ed over a column

of silica gel (12% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ

7.98 (d, 2H, J = 8.4 Hz), 7.71 (d, 2H, J = 8.4 Hz), 7.40 −7.43 (m, 3H),

7.39 (t, 1H, J = 3.6 Hz), 7.32 −7.35 (m, 1H), 7.28 (t, 2H, J = 7.6 Hz),

7.17 (t, 2H, J = 8.4 Hz), 6.70 (s, 1H), 2.31 (s, 3H); ¹³C{¹H} NMR

(CDCl₃, 100 MHz) δ 162.7, 156.4, 144.8, 141.0, 138.6, 132.2, 132.1,

131.9, 130.0, 129.34, 129.26, 128.0, 127.0, 126.2, 118.6, 21.8; IR (KBr,

cm⁻¹) 3065, 2935, 2845, 1746, 1606, 1234, 1145, 1063. MS (ESI/Q-

TOF) (m /z ) calcd for C₂₂H₁₈ClO₄S [M + H]⁺413.0609, found

413.2609.

brown solid (168 mg, 62% yield); mp 137 −139 °C; puri ﬁ ed over a

(Z)-1-Phenyl-2-tosylvinyl 4-Bromobenzoate (1eb′):

1

column of silica gel (18% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.14 (d, 1H, J = 8.4 Hz), 7.99, (d, 1H, J = 2.0 Hz), 7.69 (d, 2H, J

= 8.4 Hz), 7.41 (dd, 3H, J₁= 7.6 Hz, J₂= 1.2 Hz), 7.32−7.36 (m, 1H),

7.26 −7.30 (m, 2H), 7.16 (t, 2H, J = 8.0 Hz), 6.63 (s, 1H), 2.31 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 161.8, 155.9, 145.0, 141.7, 139.8,

138.3, 133.5, 132.1, 131.9, 130.5, 130.1, 129.3, 128.8, 128.0, 126.4,

118.3, 96.0, 21.9; IR (KBr, cm⁻¹) 3069, 2920, 2844, 1755, 1615, 1573,

1149, 1089; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₂H₁₇ClIO₄S [M

+ H]⁺538.9575, found 538.9567.

white solid (147 mg, 64% yield); mp 116 −118 °C; puri ﬁ ed over a

1

(Z)-1-Phenyl-2-tosylvinyl 2-Bromo-4-methylbenzoate (1ib′):

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 8.0 (d, 2H, J = 9.0 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.68 (d, 2H, J =

9.0 Hz), 7.49 (d, 2H, J = 7.2 Hz), 7.44 (t, 1H, J = 7.2 Hz), 7.37 (t, 2H, J

= 7.2 Hz), 7.27 (d, 2H, J = 7.2 Hz), 6.80 (s, 1H), 2.41 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 150 MHz) δ 162.9, 156.3, 144.8, 138.5, 132.3, 132.2,

132.1, 131.9, 130.0, 129.7, 129.3, 128.0, 127.4, 126.2, 118.5, 21.8; IR

(KBr, cm⁻¹) 3063, 2929, 2853, 1748, 1622, 1242, 1147, 1067; HRMS

(ESI/Q-TOF) (m /z ) calcd for C₂₂H₂₁BrO₄SN [M + NH₄]⁺457.0104,

found 457.0103.

(Z)-1-Phenyl-2-tosylvinyl 2-Bromobenzoate (1fb′):

white solid (151 mg, 64% yield); mp 139 −141 °C. ¹H NMR (CDCl₃,

400 MHz) δ 8.17 (d, 1H, J = 8.0 Hz), 7.81 (d, 2H, J = 8.0 Hz), 7.58 (s,

1H), 7.54 (d, 2H, J = 7.2 Hz), 7.43 (d, 1H, J = 7.2 Hz), 7.39 (dd, 2H, J₁

= 8.4 Hz, J₂= 6.8 Hz), 7.29 (dd, 1H, J₁= 8.0 Hz, J₂= 0.8 Hz), 7.26 (s,

1H), 7.24 (s, 1H), 6.75 (s, 1H), 2.44 (s, 3H), 2.40 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 100 MHz) 161.9, 156.4, 145.5, 144.8, 138.4, 135.7,

133.3, 132.4, 131.7, 130.0, 129.2, 128.6, 128.0, 126.4, 126.3, 123.4,

118.5, 21.9, 21.5; IR (KBr, cm⁻¹) 3060, 2912, 2850, 1757, 1601, 1229,

1146, 1076; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₃H₂₀BrO₄S [M +

H]⁺471.0260, found 471.0251.

white solid (148 mg, 65% yield); mp 105 −107 °C; puri ﬁ ed over a

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.29 (dd, 1H, J₁= 7.6 Hz, J₂= 2.0 Hz), 7.83 (d, 2H, J = 7.6 Hz),

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(Z)-1-Phenyl-2-tosylvinyl 2,4,6-Trimethylbenzoate (1jb′):

(Z)-1-Phenyl-2-tosylvinyl Octanoate (1nb′):

gummy residue (145 mg, 72% yield); puri ﬁ ed over a column of silica gel

(5% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.86 (d, 2H, J =

8.0 Hz), 7.45 (d, 1H, J = 4.4 Hz), 7.41 −7.44 (m, 2H), 7.38 (d, 2H, J =

7.6 Hz), 7.35 (d, 2H, J = 8.0 Hz), 6.62 (s, 1H), 2.66 (t, 2H, J = 7.6 Hz),

2.44 (s, 3H), 1.71 −1.78 (m, 2H), 1.28 −1.40 (m, 7H), 1.25 (s, 1H),

0.89 (t, 3H, J = 7.2 Hz); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 170.8,

156.6, 138.9, 134.8, 132.7, 131.7, 130.0, 129.2, 127.8, 126.3, 117.6, 34.2,

31.9, 31.1, 29.1, 24.6, 22.8, 21.9, 14.3; IR (KBr, cm⁻¹) 3065, 2934, 2829,

1770, 1612, 1134, 1077; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₃H₃₂O₄SN [M + NH₄]⁺418.2047, found 418.2045.

white solid (110 mg, 52% yield); mp 128 −130 °C. ¹H NMR (CDCl₃,

600 MHz) δ 7.69 (d, 2H, J = 8.4 Hz), 7.53 (d, 2H, J = 7.8 Hz), 7.44 (t,

1H, J = 7.2 Hz), 7.39 (t, 2H, J = 7.2 Hz), 7.19 (d, 2H, J = 8.4 Hz), 6.96

(s, 2H), 6.70 (s, 1H), 2.50 (s, 6H), 2.40 (s, 3H), 2.35 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 150 MHz) δ 165.4, 157.4, 144.5, 141.8, 139.6, 138.9,

133.2, 131.5, 130.1, 129.8, 129.1, 128.0, 126.8, 126.6, 119.5, 31.2, 22.2,

21.8, 21.5; IR (KBr, cm⁻¹) 3065, 2924, 1747, 1610, 1225, 1145, 1048;

HRMS (ESI/Q-TOF) (m /z ): calcd. for C₂₅H₂₈O₄SN [M + NH₄]⁺

438.1734, found 438.1732.

(Z)-1-Phenyl-2-tosylvinyl Decanoate (1ob′):

(Z)-1-Phenyl-2-tosylvinyl Acetate (1kb′):

gummy residue (103 mg, 65% yield); puri ﬁ ed over a column of silica gel

(8% EtOAc in hexane); ¹H NMR (CDCl₃, 600 MHz) δ 7.86 (d, 2H, J =

8.4 Hz), 7.45 −7.47 (m, 2H), 7.41 −7.43 (m, 1H), 7.38 (d, 2H, J = 7.8

Hz), 7.35 (d, 2H, J = 8.4 Hz), 6.64 (s, 1H),), 2.43 (s, 3H), 2.39 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 168.0, 156.3, 144.9, 138.8, 132.3,

131.8, 130.0, 129.1, 127.7, 126.2, 117.4, 21.8, 21.1; IR (KBr, cm⁻¹)

3063, 2929, 1737, 1620, 1597, 1319, 1144, 1085; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₁₇H₁₇O₄S [M + H]⁺317.0842, found 317.0858.

(Z)-1-Phenyl-2-tosylvinyl Pivalate (1lb′):

gummy residue (161 mg, 75% yield); puri ﬁ ed over a column of silica gel

(5% EtOAc in hexane); ¹H NMR (CDCl₃, 600 MHz) δ 7.88 (d, 2H, J =

8.4 Hz), 7.44 −7.47 (m, 3H), 7.40 (d, 2H, J = 7.8 Hz), 7.37 (d, 2H, J =

7.8 Hz), 6.64 (s, 1H), 2.69 (t, 2H, J = 7.2 Hz), 2.46 (s, 3H), 1.75 −1.80

(m, 2H), 1.41 −1.44 (m, 2H), 1.28 −1.32 (m, 10H), 0.91 (t, 3H, J = 7.2

Hz); ¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 170.8, 156.6, 144.8, 138.9,

132.7, 131.7, 130.0, 129.1, 127.8, 126.3, 117.6, 34.2, 32.1, 29.6, 29.49,

29.48, 29.3, 24.6, 22.9, 21.9, 14.3; IR (KBr, cm⁻¹) 3063, 2924, 2854,

1772, 1621, 1149, 1081;HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₅H₃₃O₄S [M + H]⁺429.2094, found 429.2088.

(Z)-1-Phenyl-2-tosylvinyl Stearate (1pb′):

brown solid (126 mg, 70% yield); mp 85 −87 °C; puri ﬁ ed over a column

of silica gel (5% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.86

(d, 2H, J = 8.4 Hz), 7.41 −7.46 (m, 3H), 7.39 (s, 1H), 7.33 −7.37 (m,

3H), 6.57 (s, 1H), 2.44 (s, 3H), 1.43 (s, 9H); ¹³C{¹H} NMR (CDCl₃,

100 MHz) δ , 175.4, 156.7, 144.7, 139.0, 133.2, 131.6, 130.0, 129.2,

127.7, 126.2, 117.5, 39.5, 27.5, 21.8; IR (KBr, cm⁻¹) 3063, 2925, 1759,

1622, 1480, 1262, 1150, 1078; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₀H₂₃O₄S [M + H]⁺359.1312, found 359.1309.

gummy residue (176 mg, 65% yield); puri ﬁ ed over a column of silica gel

(3% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.86 (d, 2H, J =

8.0 Hz), 7.45 (d, 1H, J = 4.4 Hz), 7.41 −7.43 (m, 2H), 7.38 (d, 2H, J =

7.6 Hz), 7.34 (d, 2H, J = 8.0 Hz), 6.62 (s, 1H), 2.66 (t, 2H, J = 7.6 Hz),

2.44 (s, 3H), 2.35 (t, 1H, J = 7.6 Hz), 1.71 −1.78 (m, 2H), 1.62 (dd, 2H,

J₁= 14.8 Hz J₂= 6.8 Hz), 1.25 (m, 25H), 0.87 (t, 3H, J = 6.8 Hz);

¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 170.8, 156.6, 144.8, 138.9, 132.7,

131.7, 130.0, 129.2, 127.8, 126.3, 117.6, 34.2, 33.9, 32.1, 29.91, 29.87,

29.8, 29.69, 29.65, 29.6, 29.50, 29.45, 29.31, 29.27, 24.9, 24.6, 22.9,

21.9, 14.3; IR (KBr, cm⁻¹) 3063, 2921, 2851, 1772, 1709, 1619, 1150,

1080; HRMS (ESI/Q-TOF) (m /z ) calcd for C₃₃H₅₂O₄SN [M +

NH₄]⁺558.3612, found 558.3612.

(Z)-1-Phenyl-2-tosylvinyl Hexanoate (1mb′):

(Z)-1-Phenyl-2-tosylvinyl 2-Cyclopropylacetate (1qb′):

gummy residue (126 mg, 68% yield); puri ﬁ ed over a column of silica gel

(5% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.86 (d, 2H, J =

8.0 Hz), 7.46 (s, 1H), 7.41 −7.44 (m, 2H), 7.38 (d, 2H, J = 7.6 Hz), 7.35

(d, 2H, J = 8.0 Hz), 6.62 (s, 1H), 2.66 (t, 2H, J = 8.0 Hz), 2.44 (s, 3H),

1.72 −1.79 (m, 2H), 1.37 −1.41 (m, 4H), 0.93 (t, 3H, J = 7.2 Hz);

¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 170.8, 156.6, 144.8, 139.0, 132.8,

131.7, 130.0, 129.2, 127.8, 126.3, 117.6, 34.2, 31.4, 24.3, 22.5, 21.9,

14.1; IR (KBr, cm⁻¹) 3065, 2925, 2852, 1765, 1638, 1159, 1075;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₁H₂₄O₄SK [M + K]⁺

411.1027, found 411.1022.

white solid (114 mg, 64% yield); mp 125 −127 °C; puri ﬁ ed over a

1

column of silica gel (3% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 7.89 (d, 2H, J = 8.4 Hz), 7.50 (d, 2H, J = 7.2 Hz), 7.46 (t, 1H, J

= 7.2 Hz), 7.41 (d, 2H, J = 7.8 Hz), 7.37 (d, 2H, J = 7.8 Hz), 6.66 (s,

1H), 2.60 (d, 2H, J = 7.2 Hz), 2.46 (s, 3H), 1.89 −1.24 (m, 1H), 0.68 (q,

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2H, J₁= 13.2 Hz, J₂= 5.4 Hz), 0.33 (q, 2H, J₁= 10.2 Hz, J₂= 4.8 Hz);

¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 170.2, 156.5, 144.8, 138.9, 132.6,

(Z)-1-Phenyl-2-tosylvinyl Thiophene-2-carboxylate (1ub′):

131.7, 130.0, 129.1, 127.8, 126.3, 117.4, 39.4, 21.9, 6.7, 4.8; IR (KBr,

cm⁻¹) 3066, 3001, 1772, 1621, 1149, 1080; HRMS (ESI/Q-TOF) (m /

z ) calcd for C₂₀H₂₄O₄SN [M + NH₄]⁺374.1421, found 374.1422.

(Z)-1-Phenyl-2-tosylvinyl (3r,5r,7r)-Adamantane-1-carboxylate

(1rb′):

white solid (106 mg, 55% yield); mp 122 −124 °C; puri ﬁ ed over a

1

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 7.97 (dd, 1H, J₁= 4.2 Hz, J₂= 1.2 Hz), 7.86 (d, 2H, J = 8.4 Hz),

7.73 (dd, 1H, J₁= 5.4 Hz, J₂= 1.2 Hz), 7.51 (d, 2H, J = 7.8 Hz), 7.43 (t,

1H, J = 7.8 Hz), 7.37 (t, 2H, J = 7.2 Hz), 7.28 (d, 2H, J = 7.8 Hz), 7.21

(dd, 1H, J₁= 4.8 Hz, J₂= 4.2 Hz), 6.80 (s, 1H), 2.41 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 150 MHz) δ 158.7, 156.1, 144.8, 138.6, 135.9, 134.6,

132.3, 131.8, 131.5, 129.9, 129.2, 128.5, 128.1, 126.3, 119.0, 21.9; IR

(KBr, cm⁻¹) 3055, 2925, 1735, 1619, 1409, 1238, 1147, 1062; HRMS

(ESI/Q-TOF) (m /z ) calcd for C₂₀H₁₇O₄S₂, [M + H]⁺385.0563, found

385.0565.

white solid (127 mg, 58% yield); mp 156 −158 °C; puri ﬁ ed over a

1

column of silica gel (3% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 7.86 (d, 2H, J = 8.4 Hz), 7.44 (t, 2H, J = 9.0 Hz), 7.41 (dd, 1H,

J₁= 7.8 Hz, J₂= 1.2 Hz), 7.37 (d, 2H, J = 7.8 Hz), 7.35 (d, 2H, J = 7.8

Hz), 6.57 (s, 1H), 2.44 (s, 3H), 2.14 (s, 6H), 2.11 (s, 3H), 1.78 (s, 6H);

¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 174.5, 156.7, 144.6, 139.0, 133.1,

131.5, 130.0, 129.1, 127.7, 126.2, 117.4, 41.4, 38.9, 36.6, 28.1, 21.9; IR

(KBr, cm⁻¹) 3060, 2907, 2852, 1757, 1623, 1176, 1149, 1047; HRMS

(ESI/Q-TOF) (m /z ) calcd for C₂₆H₂₈O₄SNa [M + Na]⁺: 459.1601,

found 459.1601.

(Z)-1-(p-Tolyl)-2-tosylvinyl 4-Methylbenzoate (2bb′):

(Z)-1-Phenyl-2-tosylvinyl Benzo[d][1,3]dioxole-5-carboxylate

(1sb′): brown solid (127 mg, 60% yield); mp 152−154°C; puriﬁed

brown solid (151 mg, 74% yield); mp 123 −125 °C; puri ﬁ ed over a

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.0 (d, 2H, J = 8.0 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.38, (d, 2H, J

= 8.0 Hz), 7.33 (d, 2H, J = 8.0 Hz), 7.23 (d, 2H, J = 8.0 Hz), 7.15 (d, 2H,

J = 8.0 Hz), 6.76 (s, 1H), 2.47 (s, 3H), 2.39 (s, 3H), 2.34 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 163.4, 157.1, 145.3, 144.5, 142.4,

138.8, 130.8, 130.4, 129.9, 129.8, 129.6, 129.4, 128.0, 126.2, 117.6, 22.0,

21.8, 21.6; IR (KBr, cm⁻¹) 3049, 2924, 1746, 1689, 1610, 1148, 1085;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₄H₂₂O₄SNa [M + Na]⁺

429.1131, found 429.1135.

over a column of silica gel (12% EtOAc in hexane); ¹H NMR (CDCl₃,

600 MHz) δ 7.74 (d, 2H, J = 7.8 Hz), 7.68 (dd, 1H, J₁= 8.4 Hz, J₂= 1.2

Hz), 7.44 (d, 1H, J = 1.8 Hz), 7.41 (d, 2H, J = 7.2 Hz), 7.35 (d, 1H, J =

7.8 Hz), 7.29 (t, 2H, J = 7.8 Hz), 7.19 (d, 2H, J = 7.8 Hz), 6.85 (d, 1H, J

= 8.4 Hz), 6.71 (s, 1H), 6.03 (s, 2H), 2.33 (s, 3H); ¹³C{¹H} NMR

(CDCl₃, 150 MHz) δ 162.7, 156.8, 152.9, 148.2, 144.7, 138.6, 132.4,

131.7, 129.9, 129.2, 128.0, 127.1, 126.2, 122.2, 118.6, 110.3, 108.5,

102.3, 21.8; IR (KBr, cm⁻¹) 3058, 2929, 1745, 1611, 1482, 1257, 1149,

1063; HRMS (ESI/Q-TOF) (m/z) calcd for C₂₃H₁₈O₆SNa [M + Na]⁺

445.0716, found 445.0715.

(Z)-1-(4-Methoxyphenyl)-2-tosylvinyl 4-Methylbenzoate (3bb′):

(Z)-1-Phenyl-2-tosylvinyl 2-Naphthoate (1tb′):

brown solid (165 mg, 78% yield); mp 128 −130 °C; puri ﬁ ed over a

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 8.01 (d, 2H, J = 8.4 Hz), 7.79 (d, 2H, J = 8.4 Hz), 7.43, (d, 2H, J

= 9.0 Hz), 7.33 (d, 2H, J = 7.8 Hz), 7.23 (d, 2H, J = 8.4 Hz), 6.85 (d, 2H,

J = 8.4 Hz), 6.70 (s, 1H), 3.80 (s, 3H), 2.48 (s, 3H), 2.39 (s, 3H),;

¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 163.3, 162.3, 156.7, 145.1, 144.2,

138.8, 132.0, 130.6, 129.6, 129.4, 127.8, 125.6, 124.4, 116.2, 114.4, 55.5,

21.9, 21.6; IR (KBr, cm⁻¹) 3066, 2925, 2853, 1745, 1602, 1156, 1087;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₄H₂₆O₅SN [M + NH₄]⁺

440.1526, found 440.1524.

(Z)-1-(4-(tert-Butyl)phenyl)-2-tosylvinyl 4-Methylbenzoate

(4bb′):

white solid (133 mg, 62% yield); mp 90 −92 °C; puri ﬁ ed over a column

of silica gel (12% EtOAc in hexane); ¹H NMR (CDCl₃, 600 MHz) δ

8.71 (s, 1H), 8.09 (dd, 1H, J₁= 8.4 Hz, J₂= 1.8 Hz), 8.01 (d, 1H, J = 7.8

Hz), 7.96 (dd, 2H, J₁= 12.6 Hz, J₂= 8.4 Hz), 7.83 (d, 2H, J = 8.4 Hz),

7.66 −7.69 (m, 1H), 7.60 −7.63 (m, 1H), 7.55 (d, 2H, J = 7.8 Hz), 7.44

(t, 1H, J = 7.2 Hz), 7.37 (t, 2H, J = 7.8 Hz), 7.22 (d, 2H, J = 7.8 Hz),

6.87 (s, 1H), 2.37 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 163.5,

156.8, 144.7, 138.6, 136.2, 132.7, 132.6, 132.4, 131.8 ̧129.9, 129.7,

129.2, 128.8, 128.5, 128.11, 128.09, 127.3, 126.3, 125.6, 125.5, 118.8,

21.8; IR (KBr, cm⁻¹) 3464, 3055, 2931, 1713, 1630, 1280, 1196, 1090;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₆H₂₄O₄SN [M + NH₄]⁺

446.1421, found 446.1412.

L

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brown solid (169 mg, 75% yield); mp 159 −161 °C; puri ﬁ ed over a

(Z)-1-(4-Fluorophenyl)-2-tosylvinyl 4-Methylbenzoate (8bb′):

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.43 (d, 2H, J =

8.4 Hz), 7.37 (s, 1H), 7.34 (t, 3H, J = 8.0 Hz), 7.23 (d, 2H, J = 8.0 Hz),

6.79 (s, 1H), 2.48 (s, 3H), 2.39 (s, 3H), 1.27 (s, 9H); ¹³C{¹H} NMR

(CDCl₃, 100 MHz) δ 163.5, 157.0, 155.4, 145.3, 144.5, 138.9, 130.8,

129.8, 129.6, 129.5, 128.0, 126.2, 126.0, 125.8, 117.8, 35.1, 31.2, 22.0,

21.8; IR (KBr, cm⁻¹) 3052, 2957, 2920, 1746, 1610, 1264, 1177, 1067;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₇H₃₂O₄SN [M + NH₄]⁺

466.2047 found 466.2047

white solid (132 mg, 64% yield); mp 142 −144 °C; puri ﬁ ed over a

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 600

(Z)-1-(m-Tolyl)-2-tosylvinyl 4-Methylbenzoate (5bb′):

1

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.79 (d, 2H, J = 8.4 Hz), 7.47 −7.50 (m,

2H), 7.33 (d, 2H, J = 8.4 Hz), 7.24 (d, 2H, J = 7.8 Hz), 7.05 (t, 2H, J =

9.0 Hz), 6.74 (s, 1H), 2.48 (s, 3H), 2.39 (s, 3H); ¹³C{¹H} NMR

(CDCl₃, 150 MHz) δ 164.8, (d, J = 100.8 Hz), 155.8, 144.8, 144.7 (d, J

= 48.1 Hz), 138.5, 130.8, 129.9, 129.7, 128.7 (d, J = 12.6), 128.52,

128.47, 128.1, 125.5, 118.6, 116.5 (d, J = 28.2 Hz), 22.1, 21.9; ¹⁹F NMR

(CDCl₃, 564 MHz) −107.4; IR (KBr, cm⁻¹) 3063, 2923, 2853, 1745,

1610, 1238, 1147, 1064; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₃H₂₃FO₄SN [M + NH₄]⁺428.1326, found 428.1320.

gummy residue (143 mg, 70% yield); puri ﬁ ed over a column of silica gel

(7% EtOAc in hexane); ¹H NMR (CDCl₃, 600 MHz) δ 8.01 (d, 2H, J =

7.8 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.33 (d, 2H, J = 7.8 Hz), 7.28 −7.30

(m, 2H), 7.23 (d, 4H, J = 7.2 Hz), 6.79 (s, 1H), 2.48 (s, 3H), 2.39 (s,

3H), 2.31 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 163.4, 157.1,

145.3, 144.6, 139.0, 138.7, 132.6, 132.5, 130.8, 129.8, 129.6, 129.1,

128.1, 126.8, 125.7, 123.4, 118.5, 22.0, 21.8, 21.6; IR (KBr, cm⁻¹) 3063,

2920, 1745, 1611, 1235, 1147, 1068; HRMS (ESI/Q-TOF) (m /z )

calcd for C₂₄H₂₃O₄S [M + H]⁺407.1312, found 407.1336.

(Z)-1-(3-Fluorophenyl)-2-tosylvinyl 4-Methylbenzoate (9bb′):

(Z)-1-(4-Chlorophenyl)-2-tosylvinyl 4-Methylbenzoate (6bb′):

white solid (126 mg, 61% yield); mp 121 −123 °C; puri ﬁ ed over a

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.01 (d, 2H, J = 8.4 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.33 (d, 3H, J

= 8.0 Hz), 7.28 −7.31 (m, 1H), 7.24 (d, 2H, J = 8.0 Hz), 7.15 −7.19 (m,

1H), 7.08 −7.14 (m, 1H), 6.80 (s, 1H), 2.48 (s, 3H), 2.39 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 163.4, 163.0 (d, J = 98.6 Hz),

155.3 (d, J = 11.2 Hz), 145.6, 144.9, 138.4, 134.9 (d, J = 30.4 Hz), 130.9,

130.8, 129.9, 129.7, 128.1, 125.4, 122.0 (d, J = 12.4 Hz), 119.8, 118.6

(d, J = 84.4 Hz), 113.3 (d, J = 38.3 Hz), 22.0, 21.8; ¹⁹F (CDCl₃, 376

MHz) −111.2; IR (KBr, cm⁻¹) 3066, 2925, 2857, 1736, 1487, 1216,

1100, 1030; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₃H₁₉FO₄SNa [M

+ Na]⁺433.0880, found 433.0898.

white solid (145 mg, 68% yield); mp 115 −117 °C; puri ﬁ ed over a

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.79, (d, 2H, J = 7.8 Hz), 7.42 (d, 2H, J

= 9.0 Hz), 7.34 (s, 2H), 7.33 (d, 2H, J = 1.8 Hz), 7.24 (d, 2H, J = 8.4

Hz), 6.78 (s, 1H), 2.48 (s, 3H), 2.39 (s, 3H); ¹³C{¹H} NMR (CDCl₃,

150 MHz) δ 163.4, 155.7, 145.6, 144.8, 138.4, 137.9, 131.1, 130.8,

129.9, 129.7, 129.5, 128.1, 127.5, 125.4, 119.1, 22.1, 21.9; IR (KBr,

cm⁻¹) 3069, 2960, 2923, 1749, 1613, 1172, 1066; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₃H₂₀ClO₄S [M + H]⁺427.0765, found

427.0767.

(Z)-1-(3-Chlorophenyl)-2-tosylvinyl 4-Methylbenzoate (10bb′):

(Z)-1-(4-Bromophenyl)-2-tosylvinyl 4-Methylbenzoate (7bb′):

white solid (139 mg, 65% yield); mp 122 −124 °C; puri ﬁ ed over a

1

column of silica gel (10% EtOAc in hexane); H NMR (CDCl₃, 400

white solid (165 mg, 70% yield); mp 162 −164 °C; puri ﬁ ed over a

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.79 (d, 2H, J = 8.0 Hz), 7.44 (t, 1H, J =

7.6 Hz), 7.35 −7.38 (m, 2H), 7.32 (d, 2H, J = 8.0 Hz), 7.29 (d, 1H, J =

8.0 Hz), 7.23 (d, 2H, J = 8.0 Hz),), 6.78 (s, 1H), 2.46 (s, 3H), 2.38 (s,

3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 163.2, 155.1, 145.4, 144.7,

138.2, 135.2, 134.4, 131.5, 130.7, 130.3, 129.8, 129.5, 128.0, 126.1,

125.2, 124.3, 119.7, 21.9, 21.7; IR (KBr, cm⁻¹) 3065, 2925, 2851, 1749,

1613, 1172, 1066; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₃H₂₃ClO₄SN [M + NH₄]⁺444.1031, found 444.1031.

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.80 (d, 2H, J = 8.4 Hz), 7.48 (d, 2H, J =

8.4 Hz), 7.34 (dd, 4H, J₁= 10.2 Hz, J₂= 7.8 Hz), 7.24 (d, 2H, J = 7.8

Hz), 6.80 (s, 1H), 2.47 (s, 3H), 2.39 (s, 3H), ¹³C{¹H} NMR (CDCl₃,

150 MHz) δ 163.3, 155.7, 145.6, 144.8, 138.3, 132.4, 131.5, 130.7,

129.9, 129.7, 128.1, 127.7, 126.3, 125.3, 119.1, 22.0, 21.8; IR (KBr,

cm⁻¹) 3069, 2960, 2923, 1749, 1613; HRMS (ESI/Q-TOF) (m /z )

calcd for C₂₃H₁₉BrO₄SNa [M + Na]⁺493.0080, found 493.0040.

M

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(Z)-1-Cyclohexyl-2-tosylvinyl 4-Methylbenzoate (11bb′):

= 7.5 Hz), 7.43 −7.46 (m, 4H), 7.37 (d, 2H, J = 8.5 Hz), 7.33 (d, 2H, J =

8.0 Hz), 6.81 (s, 1H), 2.47 (s, 3H), 1.28 (s, 9H); ¹³C{¹H} NMR

(CDCl₃, 125 MHz) δ 163.4, 157.5, 155.5, 145.3, 141.8, 133.5, 130.7,

129.6, 129.4, 129.1, 127.9, 126.2, 126.1, 125.7, 117.5, 35.1, 31.2, 22.0;

IR (KBr, cm⁻¹) 3052, 2988, 1745, 1611, 1261, 1065; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₆H₃₀O₄SN [M + NH₄]⁺452.1901, found

452.1898.

(Z)-1-(4-Bromophenyl)-2-(phenylsulfonyl)vinyl 4-Methylben-

zoate (7ba′):

gummy residue (142 mg, 71% yield); puri ﬁ ed over a column of silica gel

(5% EtOAc in hexane); ¹H NMR (CDCl₃, 500 MHz) δ 7.93 (d, 2H, J =

7.5 Hz), 7.72 (d, 2H, J = 7.5 Hz), 7.28 (d, 2H, J = 7.5 Hz), 7.23 (d, 2H, J

= 7.5 Hz), 6.17 (s, 1H), 2.44 (s, 3H), 2.39 (s, 3H), 1.63 −1.67 (m, 2H),

1.59 (s, 4H), 0.90 (t, 3H, J = 11.5 Hz), 0.83 (d, 2H, J = 3.5 Hz);

¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 163.6, 162.5, 145.1, 144.3, 138.9,

130.7, 129.8, 129.5, 127.9, 126.0, 116.4, 29.90, 29.87, 22.0, 21.8, 15.9,

7.08; IR (KBr, cm⁻¹) 3058, 2915, 2824, 1748, 1619, 1152, 1035.;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₃H₂₇O₄S [M + H]⁺399.1625,

found 399.1680.

(Z)-1-((1-Iodo-1-phenylprop-1-en-2-yl)sulfonyl)-4-methylben-

zene (12b′):

brown solid (157 mg, 68% yield); mp 157 −159 °C; puri ﬁ ed over a

1

column of silica gel (10% EtOAc in hexane); H NMR (CDCl₃, 500

MHz) δ 7.95 (d, 2H, J = 5.5 Hz), 7.88 (d, 2H, J = 7.0 Hz), 7.50 (d, 1H, J

= 7.5 Hz), 7.44 (d, 2H, J = 6.5 Hz),), 7.35 −7.40 (m, 3H), 7.29 (t, 2H, J

= 8.5 Hz), 7.21 (d, 1H, J = 7.0 Hz), 6.77 (s, 1H), 2.41 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 125 MHz) δ 163.4, 157.4, 145.4, 141.6, 133.6, 132.4,

131.8, 130.8, 129.7, 129.20, 129.17, 128.0, 126.3, 125.6, 118.4, 22.0; IR

(KBr, cm⁻¹) 3065, 2959, 2928, 1745, 1610; HRMS (ESI/Q-TOF) (m /

z ) calcd for C₂₂H₂₁BrO₄SN [M + NH₄]⁺474.0380, found 474.0358.

(Z)-2-((4-(tert-Butyl)phenyl)sulfonyl)-1-phenylvinyl 4-Methylben-

zoate (1bc′):

brown solid (161 mg, 80% yield); mp 120 −122 °C; puri ﬁ ed over a

1

column of silica gel (3% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 7.39 (d, 2H, J = 8.4 Hz), 7.23 (t, 3H, J = 6.5 Hz), 7.16 (d, 2H, J

= 8.0 Hz), 7.09 −7.12 (m, 2H), 2.51 (s, 3H), 2.39 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 100 MHz) δ 144.3, 144.1, 143.2, 137.5, 129.7, 128.8,

128.0, 127.84, 127.76, 115.9, 27.3. 21.8; IR (KBr, cm⁻¹) 3035, 2928,

2847, 1587, 1442, 1135, 1080; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₁₆H₁₉IO₂SN [M + NH₄]⁺416.0187, found 416.0183.

(Z)-2-(Phenylsulfonyl)-1-(p-tolyl)vinyl 4-Methylbenzoate (2ba′):

gummy residue (162 mg, 74% yield); puri ﬁ ed over a column of silica gel

(15% EtOAc in hexane); ¹H NMR (CDCl₃, 500 MHz) δ 8.0, (d, 2H, J =

5.0 Hz), 7.84 (d, 2H, J = 8.5 Hz), 7.49 (t, 2H, J = 8.0 Hz), 7.43 (t, 3H, J

= 12.0 Hz), 7.34 (dd, 4H, J₁= 18.0 Hz, J₂= 7.5 Hz), 6.82 (s, 1H), 2.48

(s, 3H), 1.30 (s, 9H); ¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 163.4,

157.5, 156.8, 145.4, 138.5, 132.6, 131.7, 130.8, 129.6, 129.2, 127.9,

126.26, 126.25, 125.7, 118.8, 35.4, 31.2, 22.0; IR (KBr, cm⁻¹) 3064,

2928, 2905, 1745, 1618; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₆H₂₇O₄S [M + H]⁺435.1625, found 435.1611.

brown solid (139 mg, 70% yield); mp 132 −134 °C; puri ﬁ ed over a

1

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 8.0 (d, 2H, J = 8.4 Hz), 7.93 (d, 2H, J = 8.0 Hz), 7.56 (t, 1H, J =

7.6 Hz), 7.44, (t, 2H, J = 8.0 Hz), 7.39 (d, 2H, J = 8.4 Hz), 7.33 (d, 2H, J

= 8.4 Hz), 7.16 (d, 2H, J = 8.0 Hz), 6.78 (s, 1H), 2.47 (s, 3H), 2.39 (s,

3H), 2.34 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 163.4, 157.6,

145.4, 142.5, 141.8, 133.5, 130.8, 130.0, 129.6, 129.5, 129.2, 128.0,

126.2, 125.7, 117.4, 22.0, 21.6; IR (KBr, cm⁻¹) 3056, 2925, 1744, 1611,

1261, 1055; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₃H₂₄O₄SN [M +

NH₄]⁺410.1432, found 410.1431.

(Z)-2-((4-Chlorophenyl)sulfonyl)-1-phenylvinyl 4-Methylben-

zoate (1bd′):

(Z)-1-(4-(tert-Butyl)phenyl)-2-(phenylsulfonyl)vinyl 4-Methylben-

zoate (4ba′):

white solid (137 mg, 66% yield); mp 142 −149 °C; puri ﬁ ed over a

1

column of silica gel (10% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 7.99 (d, 2H, J = 8.0 Hz), 7.85 (d, 2H, J = 8.4 Hz), 7.50 (d, 3H, J

= 7.6 Hz), 7.39 (d, 2H, J = 2.8 Hz), 7.35 (t, 4H, J = 8.0 Hz), 6.79 (s,

1H), 2.48 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 163.4, 157.8,

145.7, 140.4, 140.1, 132.3, 132.0, 130.8, 129.8, 129.6, 129.3, 129.2,

126.4, 125.5, 118.1, 22.1; IR (KBr, cm⁻¹) 3062, 2929, 2908, 1744,

1618; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₂H₂₁ClO₄SN [M +

NH₄]⁺430.0874, found 430.0854.

brown solid (152 mg, 72% yield); mp 160 −162 °C; puri ﬁ ed over a

1

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 500

MHz) δ 8.01, (d, 2H, J = 8.5 Hz), 7.94 (d, 2H, J = 8.0 Hz), 7.55 (t, 1H, J

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(Z)-2-((4-Bromophenyl)sulfonyl)-1-phenylvinyl 4-Methylben-

zoate (1be′):

(Z)-2-((4-Nitrophenyl)sulfonyl)-1-phenylvinyl 4-Methylbenzoate

(1bf′):

white solid (139 mg, 58% yield); mp 145 −147 °C; puri ﬁ ed over a

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 400

white solid (154 mg, 67% yield); mp 120 −122 °C; puri ﬁ ed over a

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 400

1

MHz) δ 7.91, (dd, 1H, J₁= 8.0 Hz, J₂= 1.2 Hz), 7.75 (d, 2H, J = 8.0 Hz),

7.64 (d, 1H, J = 8.0 Hz), 7.45, (d, 2H, J = 7.6 Hz), 7.36 (d, 1H, J = 7.2

Hz), 7.31 (d, 2H, J = 7.6 Hz), 7. Twenty-seven (dd, 1H, J₁= 7.6 Hz, J₂=

1.2 Hz),), 7.19 (d, 2H, J₁= 7.6 Hz), 7.10 (t, 1H, J = 7.6 Hz), 7.04 (s,

1H), 2.38 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 162.7, 158.2,

145.5, 141.0, 135.4, 134.4, 131.4, 130.7, 129.6, 129.3, 127.5, 126.4,

121.2, 118.0. 22.0; IR (KBr, cm⁻¹) 3065, 2938, 2935, 1744, 1610;

HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₂H₁₇NO₆SNa [M + Na]⁺

446.0669, found 446.2684.

MHz) δ 7.99 (d, 2H, J = 8.0 Hz), 7.78 (d, 2H, J = 8.8 Hz), 7.57 (d, 2H, J

= 8.8 Hz), 7.50, (d, 2H, J = 7.6 Hz), 7.44 (t, 1H, J = 7.2 Hz), 7.38 (d, 2H,

J = 7.6 Hz), 7.34 (d, 2H, J = 7.6 Hz), 6.79 (s, 1H), 2.48 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 163.3, 157.8, 145.7, 140.6, 132.6,

132.3, 132.0, 130.8, 129.8, 129.6, 129.3, 128.9, 126.3, 125.5, 118.0,

22.1; IR (KBr, cm⁻¹) 3068, 2965, 2923, 1745, 1610; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₂H₁₇BrO₄SK [M + K]⁺494.9673, found

494.9663.

(Z)-1-(4-Bromophenyl)-2-(phenylsulfonyl)vinyl 4-Methoxyben-

zoate (1ce′):

(Z)-2-((2-Bromo-4-(triﬂuoromethyl)phenyl)sulfonyl)-1-phenyl-

vinyl 4-Methylbenzoate (1bg′):

white solid (131 mg, 50% yield); mp 132 −135 °C; puri ﬁ ed over a

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 400

white solid (173 mg, 73% yield); mp 138 −140 °C; puri ﬁ ed over a

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 400

1

MHz) δ ), 8.08 (d, 1H, J = 8.0 Hz), 7.96, (s, 1H), 7.77 (d, 2H, J = 8.4

Hz), 7.53 (d, 2H, J = 7.6 Hz), 7.46 (d, 1H, J = 7.6 Hz), 7.35 −7.42 (m,

3H), 7.28 (s, 1H),), 7.26 (s, 1H), 7.10 (s, 1H), 2.47 (s, 3H); ¹³C{¹H}

NMR (CDCl₃, 100 MHz) δ 162.6, 159.1, 145.9, 144.3, 136.1, 135.8,

132.4 (q, J = 30.4 Hz), 132.3, 132.1, 132.0, 130.6, 129.7, 129.4, 126.5,

125.0, 124.5 (q, J = 29.6 Hz), 122.0, 117.2, 22.1; ¹⁹F NMR (CDCl₃, 376

MHz) −63.30; IR (KBr, cm⁻¹) 3064, 2928, 2915, 1743, 1625; HRMS

(ESI/Q-TOF) (m /z ) calcd for C₂₃H₂₀BrF₃O₄SN [M + NH₄]⁺

542.0243, found 542.0230.

MHz) δ 8.05 (d, 2H, J = 8.8 Hz), 7.78 (d, 2H, J = 8.4 Hz), 7.57 (d, 2H, J

= 8.4 Hz), 7.50, (d, 2H, J = 7.6 Hz), 7.43 (d, 1H, J = 7.6 Hz), 7.36 (t, 2H,

J = 7.2 Hz), 7.01 (d, 2H, J = 8.8 Hz), 6.79 (s, 1H), 3.92 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 164.7, 162.9, 157.8, 140.6, 132.9,

132.5, 132.3, 131.9, 129.6, 129.2, 128.9, 126.3, 120.4, 118.0, 114.4,

55.8; IR (KBr, cm⁻¹) 3069, 2948, 2925, 1747, 1628; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₂H₂₁BrO₅SN [M + NH₄]⁺490.0329, found

490.0310.

(Z)-1-(4-Bromophenyl)-2-(phenylsulfonyl)vinyl 4-Chloroben-

zoate (1de′):

(Z)-1-Phenyl-2-(thiophen-2-ylsulfonyl)vinyl 4-Methylbenzoate

(1bh′):

white solid (150 mg, 62% yield); mp 125 −127 °C; puri ﬁ ed over a

column of silica gel (12% EtOAc in hexane); H NMR (CDCl₃, 400

brown solid (100 mg, 52% yield); mp 158 −160 °C; puri ﬁ ed over a

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 500

1

MHz) δ 8.06 (d, 2H, J = 8.5 Hz), 7.78 (d, 2H, J = 8.5 Hz), 7.61 (d, 2H, J

= 8.5 Hz), 7.53 (d, 2H, J = 8.0 Hz), 7.50 (d, 2H, J = 7.5 Hz), 7.45 (d, 1H,

J = 7.0 Hz), 7.39 (t, 2H, J = 7.5 Hz), 6.78 (s, 1H), ¹³C{¹H} NMR

(CDCl₃, 100 MHz) δ 162.6, 157.2, 141.3, 140.5, 132.7, 132.2, 132.04,

132.01, 129.50, 129.47, 129.4, 129.1, 126.8, 126.3, 117.8; IR (KBr,

cm⁻¹) 3058, 2925, 2912, 1742, 1628, 1158, 1050; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₁H₁₈BrClO₄SN [M + NH₄]⁺493.9834, found

493.9834.

MHz) δ 8.08 (d, 2H, J = 8.0 Hz), 7.69 (d, 1H, J = 4.0 Hz), 7.65 (d, 1H, J

= 5.0 Hz), 7.53 (d, 2H, J = 7.5 Hz), 7.44 (t, 1H, J = 12.0 Hz), 7. 38 (d,

2H, J = 7.5 Hz), 7.34 (d, 2H, J = 9.5 Hz), 7.06 (t, 1H, J = 9.0 Hz), 6.86

(s, 1H), 2.47 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 163.5,

157.5, 145.5, 143.1, 134.04, 134.0, 132.5, 131.9, 130.9, 129.7, 129.3,

127.9, 126.4, 125.7, 118.6, 22.0; IR (KBr, cm⁻¹) 3059, 2928, 2915,

1742, 1625; HRMS (ESI/Q-TOF) (m /z ) calcd for C₂₀H₁₇O₄S₂, [M +

H]⁺385.0563, found 385.0562.

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(Z)-2-(Methylsulfonyl)-1-phenylvinyl 4-Methylbenzoate (1bi′):

(Z)-1-((2-Iodo-2-phenylvinyl)sulfonyl)-4-methylbenzene (B):^12g

brown solid (2 mmol scale, 560 mg, 74 %); mp 80 −82 °C; puri ﬁ ed over

a column of silica gel (5% EtOAc in hexane); ¹H NMR (CDCl₃, 400

MHz) δ 7.38 (d, 2H, J = 8.4 Hz), 7.29 (s, 1H), 7.22 (dd, 3H, J₁= 15.6

Hz, J₂= 8.0 Hz), 7.15 (d, 2H, J = 6.4 Hz), 7.11 (d, 2H, J = 8.0 Hz), 2.32

(s, 3H); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 144.8, 141.4, 139.8,

137.5, 130.0, 129.9, 128.1, 128.0, 127.9, 114.4, 21.8; IR (KBr, cm⁻¹)

3038, 2923, 2847, 1585, 1443, 1149, 1084; HRMS (ESI/Q-TOF) (m /

z ) calcd for C₁₅H₁₄IO₂S [M + H]⁺384.9754, found 384.9751.

2,6-Di-tert-Butyl-4-(tosylmethyl)phenol (M):

gummy residue (111 mg, 70% yield); puri ﬁ ed over a column of silica gel

(9% EtOAc in hexane); ¹H NMR (CDCl₃, 500 MHz) δ 8.08 (d, 2H, J =

7.5 Hz), 7.58 (d, 2H, J = 8.0 Hz), 7.42 (t, 2H, J = 7.5 Hz), 7.33 (d, 2H, J

= 7.5 Hz), 6.72 (s, 1H), 3.11 (s, 3H), 2.46 (s, 3H); ¹³C{¹H} NMR

(CDCl₃, 125 MHz) δ 163.8, 158.1, 145.6, 132.4, 132.0, 130.8, 129.8,

129.3, 126.4, 125.6, 117.0, 43.8, 22.0; IR (KBr, cm⁻¹) 3059, 2924, 2912,

1744; HRMS (ESI/Q-TOF) (m /z ) calcd for C₁₇H₁₆O₄SNa [M + Na]⁺

339.0662, found 339.0688.

(Z)-1-Methyl-4-((2-thiocyanato-2-(p-tolyl)vinyl)sulfonyl)benzene

(2vb′):

white solid (122 mg, 65% yield); mp 102 −104 °C; puri ﬁ ed over a

1

column of silica gel (3% EtOAc in hexane); H NMR (CDCl₃, 400

MHz) δ 7.44 (d, 2H, J = 8.4 Hz), 7.21 (d, 2H, J = 8.0 Hz), 6.73 (s, 2H),

5.24 (s, 1H), 4.19 (s, 2H), 2.40 (s, 3H), 1.31 (s, 18H); ¹³C{¹H} NMR

(CDCl₃, 100 MHz) δ 154.4, 144.5, 136.2, 135.1, 129.5, 129.1, 127.9,

119.1, 63.4, 34.3, 30.2, 21.7; IR (KBr, cm⁻¹) 3631, 3585, 2957, 1597,

1435, 1316, 1299, 1148, 1086; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₂₂H₃₄O₃SN [M + NH₄]⁺: 392.2254, found 392.2258.

brown solid (91 mg, 55% yield); mp 136 −138 °C; puri ﬁ ed over a

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 500

1

MHz) δ 7.89 (d, 2H, J = 8.0 Hz), 7.40 (d, 2H, J = 8.0 Hz), 7.24 (dd, 4H,

J₁= 16.5 Hz, J₂= 8.0 Hz), 6.64 (s, 1H), 2.48 (s, 3H), 2.37 (s, 3H);

¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 145.9, 145.6, 142.3, 137.0, 132.6,

130.4, 130.1, 129.9, 128.3, 127.8, 108.5, 21.9, 21.6; IR (KBr, cm⁻¹)

3388, 2948, 2257, 1637, 1436; HRMS (ESI/Q-TOF) (m /z ) calcd for

C₁₇H₁₅NO₂S₂K [M + K]⁺368.0187, found 368.0176.

1-Phenyl-2-tosylethan-1-one (X):

(Z)-1-(tert-Butyl)-4-(1-thiocyanato-2-tosylvinyl)benzene (4vb′):

brown solid (110 mg, 80% yield); mp 110 −112 °C; puri ﬁ ed over a

1

column of silica gel (15% EtOAc in hexane); H NMR (CDCl₃, 600

MHz) δ 7.95 (d, 2H, J = 7.2 Hz), 7.76 (d, 2H, J = 8.4 Hz), 7.62 (t, 1H, J

= 7.2 Hz), 7.48 (t, 2H, J = 7.8 Hz), 7.34 (d, 2H, J = 7.8 Hz), 4.72 (s,

2H), 2.44 (s, 3H); ¹³C{¹H} NMR (CDCl₃, 150 MHz) δ 188.4, 145.6,

135.93, 135.88, 134.6, 130.0, 129.6, 129.1, 128.8, 63.8, 21.9; IR (KBr,

cm⁻¹) 3052, 1679, 1597, 1445, 1323, 1158, 1087; HRMS (ESI/Q-

TOF) (m /z ) calcd for C₁₅H₁₅O₃S [M + H]⁺275.0736, found 275.0730.

N-Butyl-4-methylbenzamide (Y).

brown solid (109 mg, 58% yield); mp 142 −144 °C; puri ﬁ ed over a

column of silica gel (8% EtOAc in hexane); H NMR (CDCl₃, 500

1

MHz) δ 7.90, (d, 2H, J = 8.0 Hz), 7.44 (t, 2H, J = 8.5 Hz), 7.41 (d, 2H, J

= 8.0 Hz), 7.35 (dd, 2H, J₁= 6.5 Hz, J₂= 2.0 Hz), 6.65 (s, 1H), 2.49 (s,

3H), 1.31 (s, 9H); ¹³C{¹H} NMR (CDCl₃, 125 MHz) δ 155.5, 145.9,

145.4, 137.1, 132.6, 130.5, 130.3, 128.2, 127.9, 126.2, 108.5, 35.2, 31.3,

22.0; IR (KBr, cm⁻¹) 3368, 2975, 2265, 1686, 1484 HRMS (ESI/Q-

TOF) (m /z ) calcd for C₂₀H₂₁NO₂S₂K [M + K]⁺: 410.0656, found

410.0655.

gummy residue (62 mg, 65% yield); puri ﬁ ed over a column of silica gel

(8% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.65 (d, 2H, J =

8.4 Hz), 7.22 (d, 2H, J = 8.0 Hz), 6.1 (s, 1H), 3.44 (dd, 2H, J₁= 9.6 Hz,

J₂= 7.2 Hz), 2.38 (s, 3H), 1.55−1.63 (m, 2H), 1.36 −1.45 (m, 2H), 0.95

(t, 3H, J = 7.6 Hz); ¹³C{¹H} NMR (CDCl₃, 100 MHz) δ 167.7, 141.9,

132.2, 129.4, 127.0, 39.9, 32.0, 21.6, 20.4, 14.0; IR (KBr, cm⁻¹) 3314,

2957, 2929, 1631, 1543, 1305, 1153; HRMS (ESI/Q-TOF) (m /z )

calcd for C₁₂H₁₈NO, [M + H]⁺: 192.1383, found 192.1383.

Sodium 4-Nitrobenzenesulﬁnate (f′):

(Z)-1-Methyl-3-(2-(phenylsulfonyl)-1-thiocyanatovinyl)benzene

(5va′):

gummy residue (90 mg, 54% yield); puri ﬁ ed over a column of silica gel

(8% EtOAc in hexane); ¹H NMR (CDCl₃, 400 MHz) δ 7.55 (t, 2H, J =

8.0 Hz), 7.95, (d, 2H, J = 8.0 Hz), 7.65 (t, 1H, J = 7.2 Hz), 7.24 (t, 2H, J

= 5.6 Hz), 7.10 (d, 2H, J = 11.2 Hz),), 6.58 (s, 1H), 2.30 (s, 3H);

¹³C{¹H}NMR (CDCl₃, 100 MHz) δ 146.4, 140.0, 139.3, 135.4, 134.7,

132.5, 130.0, 129.9, 129.1, 128.8, 127.8, 125.5, 108.3, 21.5; IR (KBr,

cm⁻¹) 3387, 2946, 2257, 1637, 1435; HRMS (ESI/Q-TOF) (m /z )

calcd for C₁₆H₁₃NO₂S₂Na [M + Na]⁺: 333.0737, found 333.0710.

white solid (2 mmol scale, 384 mg, 92 %); ¹H NMR (D₂O, 500 MHz) δ

7.81 (d, 1H, J = 6.5 Hz), 7.62 (t, 2H, J = 7.0 Hz), 7.41 (s, 1H; ¹³C{¹H}

NMR (D₂O, 125 MHz) δ 133.2, 132.2, 128.6, 123.7.

Sodium 2-Bromo-4-(triﬂuoromethyl)benzenesulﬁnate (g′):

P

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J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry

pubs.acs.org/joc

Article

white solid (2 mmol scale, 547 mg, 88 %); ¹H NMR (D₂O, 500 MHz) δ

8.08 (s, 1H), 7.95 (q, 2H, J = 8.5 Hz); ¹³C{¹H} NMR (D₂O, 125 MHz)

δ 130.3, 130.2, 125.5 (q, J = 11.5 Hz), 124.41, 124.36, 120.9, 120.6; ¹⁹F

NMR (D₂O, 470 MHz) δ −62.5.

Tushar K. Sahu and Manoj K. Mohanta for CV experiments. We

also thank the IITG central instrument facilities for the

spectroscopic support.

Sodium Thiophene-2-sulﬁnate (h′):

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ASSOCIATED CONTENT

* Supporting Information

The Supporting Information is available free of charge at

https://pubs.acs.org/doi/10.1021/acs.joc.1c01350.

■

sı

Reaction setup, mechanistic investigations, SV and CV

graphs, X-ray crystallography description, and copies of

NMR spectra (¹H, ¹³C{¹H}, and ¹⁹F) of all compounds

(PDF)

FAIR data, including the primary NMR FID ﬁles, for

compounds 1dz (ZIP)

Accession Codes

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CCDC 2057146 contains the supplementary crystallographic

data for this paper. These data can be obtained free of charge via

www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_

request@ccdc.cam.ac.uk, or by contacting Cambridge Crystallo-

graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;

fax: + 44 1223 336033.

AUTHOR INFORMATION

Corresponding Author

■

Bhisma K. Patel − Department of Chemistry, Indian Institute of

Technology Guwahati, Guwahati, Assam 781039, India;

orcid.org/0000-0002-4170-8166; Email: patel@iitg.ac.in

Authors

Ashish Kumar Sahoo − Department of Chemistry, Indian

Institute of Technology Guwahati, Guwahati, Assam 781039,

India

Anjali Dahiya − Department of Chemistry, Indian Institute of

Technology Guwahati, Guwahati, Assam 781039, India

Bubul Das − Department of Chemistry, Indian Institute of

Technology Guwahati, Guwahati, Assam 781039, India

Ahalya Behera − Department of Chemistry, Indian Institute of

Technology Guwahati, Guwahati, Assam 781039, India

Complete contact information is available at:

https://pubs.acs.org/10.1021/acs.joc.1c01350

Notes

The authors declare no competing ﬁnancial interest.

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S

https://doi.org/10.1021/acs.joc.1c01350

J. Org. Chem. XXXX, XXX, XXX−XXX

Article Doi

Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of β-Substituted Vinylsulfones Using O- And S-Centered Nucleophiles

DOI: 10.1021/acs.joc.1c01350

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Full text of DOI:10.1021/acs.joc.1c01350

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