α-Phosphonovinyl Arylsulfonates: An Attractive Partner for the Synthesis of α-Substituted Vinylphosphonates through Palladium-Catalyzed Suzuki Reactions

Article abstract of DOI:10.1002/ejoc.201600056

It has been demonstrated that a variety of α-phosphonovinyl arylsulfonates with electron-neutral, -donating, and -withdrawing groups on the phenyl ring could be conveniently and efficiently prepared. In the presence of a Pd(OAc)₂/SPhos-based catalyst, various organoboron compounds could be employed as the nucleophilic coupling partners, such as organoboronic acids, boronate esters, and organotrifluoroborates. The newly developed O-centered electrophiles could couple with a multitude of aryl, heteroaryl, and alkylboron reagents, to give α-substituted vinylphosphonates in moderate to excellent yields. Generally, the Suzuki reaction is tolerant of extensive substitution at the aromatic ring of both electrophilic and nucleophilic coupling partners. As in the case of the Suzuki reaction of 8-quinolineboronic acid, proper choice of α-phosphonovinyl arylsulfonates is critical to efficient coupling. Moreover, the prospect for application of this method to complex synthesis has been demonstrated through the coupling of estrone-derived arylborons. The present protocol also features mild conditions and high efficiency. A new and attractive coupling partner for the synthesis of α-substituted vinylphosphonates through Suzuki reactions has been developed. The developed O-centered electrophiles couple with various organoboron reagents to give α-substituted vinylphosphonates in moderate to excellent yields. This protocol features broad substrate scope, mild conditions, and high efficiency.

Full text of DOI:10.1002/ejoc.201600056

DOI: 10.1002/ejoc.201600056
Full Paper
Cross Coupling
α-Phosphonovinyl Arylsulfonates: An Attractive Partner for the
Synthesis of α-Substituted Vinylphosphonates through
Palladium-Catalyzed Suzuki Reactions
Yewen Fang,*[a] Li Zhang,[b] Xiaoping Jin,*[c] Jinjian Li,[a] Meijuan Yuan,[b] Ruifeng Li,*[b]
Tong Wang,[a] Tao Wang,[a] Hanjun Hu,[a] and Juejun Gu[a]
Abstract: It has been demonstrated that a variety of α-phos- Generally, the Suzuki reaction is tolerant of extensive substitu-
phonovinyl arylsulfonates with electron-neutral, -donating, and tion at the aromatic ring of both electrophilic and nucleophilic
-withdrawing groups on the phenyl ring could be conveniently coupling partners. As in the case of the Suzuki reaction of 8-
and efficiently prepared. In the presence of a Pd(OAc)2/SPhos- quinolineboronic acid, proper choice of α-phosphonovinyl aryl-
based catalyst, various organoboron compounds could be em- sulfonates is critical to efficient coupling. Moreover, the
ployed as the nucleophilic coupling partners, such as organo- prospect for application of this method to complex synthesis
boronic acids, boronate esters, and organotrifluoroborates. The has been demonstrated through the coupling of estrone-de-
newly developed O-centered electrophiles could couple with a rived arylborons. The present protocol also features mild condi-
multitude of aryl, heteroaryl, and alkylboron reagents, to give α- tions and high efficiency.
substituted vinylphosphonates in moderate to excellent yields.
Introduction
ate and formaldehyde,[8] and the decarboxylative condensation
of 2-diethoxyphosphorylalkanoic acids with formaldehyde.[9]
Other methods that use ionic substitution reactions,[10] thermal
elimination of sulfinylphosphonates, and rearrangement of
benzyl(dimethoxyphosphoryl)carbene[11] have also been re-
ported. Reaction between (trimethylsilyl)diazomethane and
functionalized arylketenes affords the corresponding vinylphos-
phonate after decarbonylation.[12] Additional processes include
the Michaelis–Arbuzov type reaction of copper(I) bromide to
trialkyl phosphates with vinylic halides,[13] and the Abramov
base-catalyzed addition of dialkyl phosphites to acylarenes.[14]
Despite progress in this field, efficient methodologies applica-
ble to readily available substrates, which are operational sim-
plicity, show functional-group tolerance, and are environmental
sustainable are still highly desirable. In light of high efficiency
and atom economy, transition-metal-catalyzed hydrophosphor-
ylation reaction of terminal alkynes became an interesting strat-
egy.[15,16] However, the addition reactions of P–H bonds to triple
bonds led to a mixture of α- and ꢀ-alkenylphosphonates. Ex-
pectedly, the issue of regioselectivities could be addressed with
C–P or C–C cross-coupling reactions as the strategy. Unfortu-
nately, examples of transition-metal-catalyzed synthesis of α-
substituted vinylphosphonates by C–P cross-coupling reactions
are still rare.[17] As for the C–C bond formation reactions, great
efforts were devoted to the synthesis of internal vinylphos-
phonates by Suzuki–Miyaura[18–20] or Stille[21] cross-coupling re-
actions. Very recently, the Wang group reported that α-substi-
tuted vinylphosphonates could be obtained through Pd-cata-
lyzed coupling reaction of N-tosylhydrazones and aryl brom-
ides.[22] Relative to Stille coupling reactions and arylations of N-
tosylhydrazones, Suzuki–Miyaura reactions are more attractive
α-Substituted vinylphosphonates are an important class of or-
ganophosphorus compounds.[1] They are ubiquitous in natural
products, pharmacologically active compounds, polymer, and
other useful materials. Moreover, they are valuable synthetic
intermediates in organic transformations, such as hydrogen-
ation,[2] Heck,[3] epoxidation,[4] and Michael addition reactions[5]
because they provide efficient synthetic routes to various im-
portant organophosphorus compounds.
As a result of the importance of α-substituted vinylphos-
phonates, many synthetic methods are well elaborated. Con-
ventional methods for the synthesis of these compounds in-
volve the addition of alkyl phosphites to ꢀ-nitrostyrene fol-
lowed by ꢀ-elimination of nitrous acid,[1,6] esterification of α-
substituted vinylphosphonic acids derived from the Conant re-
action,[2a,6b] the Wittig reaction of 1-oxoalkylphosphonates with
methylenetriphenylphosphoranes,[7] the reaction of Ivanov-like
reagents derived from the reaction between benzylphosphon-
[a] School of Chemical Engineering, Ningbo University of Technology,
No. 89 Cuibai Rd., Ningbo 315016, P. R. China
E-mail: fang@nbut.edu.cn
hgxy.nbut.edu.cn
[b] College of Chemistry and Chemical Engineering,
Taiyuan University of Technology,
No. 79 West Yingze Street, Taiyuan 030024, P. R. China
E-mail: rfli@tyut.edu.cn
[c] Department of Biology and Pharmaceutical Sciences, Institution Zhejiang
Pharmaceutical College,
No. 888 Yinxian Avenue East, Ningbo 315100, P. R. China
E-mail: jinxp@mail.zjpc.net.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600056.
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Scheme 1. Synthetic steps: α-phosphonovinyl sulfonates versus α-halovinylphosphonates.
because the boron byproducts are of relatively low toxicity, the Results and Discussion
reaction tolerates a wide range of functional groups, and uses
Based on our previous report, we hypothesized that the leav-
ing-group ability of arylsulfonates in the first step (oxidative
addition) of the catalytic cycle could possibly be tuned by vary-
ing the substituent on the phenyl ring of the arylsulfonates.
Consequently, our initial effort was focused on the synthesis of
various α-phosphonovinyl arylsulfonates by adaptation of the
Doğan method.[5a] Fortunately, the procedures were amenable
to scale up, which provided desired products 5–7 in moderate
to good yields at 10 mmol scale as shown in Table 1. By treat-
ment of acetyl phosphonates 1–3 with 1,8-diazabicyclo-
[5.4.0]undec-7-ene (DBU) and various commercially available
arylsulfonyl chlorides 4, which have different substituents on
the phenyl ring, a series of α-phosphonovinyl arylsulfonates
were easily prepared in 40–89 % yields. With the exception of
6a, 6c, and 6f, arylsufonates 5–7 are highly crystalline free-flow-
ing solids.
mild reaction conditions and readily available organoboron
compounds.[23] Consequently, there is great demand and op-
portunity to develop new synthetic protocols for the synthesis
of α-substituted vinylphosphonates through coupling reactions
between organoboron reagents and α-(pseudo)halovinylphos-
phonates.
Recently, as a part of our continuing interest in transition-
metal-catalyzed cross-coupling reactions,[24,25] we conducted
on the synthesis of terminal vinylphosphonates under palla-
dium-catalyzed Suzuki–Miyaura cross-coupling reaction condi-
tions.[26] With α-(pseudo)halovinylphosphonates as the electro-
philic coupling partner,[26a,26c] a range of α-aryl vinylphosphon-
ates were efficiently prepared under palladium-catalyzed Suzuki
reaction conditions. From the viewpoint of step and atom econ-
omy, O-based electrophiles are more attractive than α-halovin-
ylphosphonates,[27] which require at least four steps from start-
ing materials (Scheme 1). Relative to nonaflates (Nf),[26c,28] cor-
Having accomplished the synthesis of α-phosphonovinyl
responding enol-derived arylsulfonates have advantages in arylsulfonates, we embarked on their applications in Suzuki re-
handling, economy, and stability. In this paper, we report the actions under our previously optimized conditions. By using a
synthesis of various α-phosphonovinyl arylsulfonates and de- catalyst composed of Pd(OAc)2 (7 mol-%)/2-dicyclohexylphos-
scribe an overview of the palladium-catalyzed Suzuki–Miyaura phino-2′,6′-dimethoxybiphenyl (SPhos; 15 mol-%), reaction of
cross-coupling reactions of α-phosphonovinyl arylsulfonates α-phosphonovinyl arylsulfonate and PhB(OH)2 (2 equiv.) was
with aryl, heteroaryl, and alkylboron reagents. A notable feature conducted at room temperature in the presence of Cs2CO3
of our methodology is the use of the easily available coupling (2.5 equiv.) in toluene.[26a] Generally, the reactions of arylsulfon-
partners in combination with a palladium catalyst under mild ates with either electron-neutral, -donating, or -withdrawing
reaction conditions.
groups at the para-position on the phenyl ring did not signifi-
Table 1. Preparation of α-phosphonovinyl arylsulfonates 5–7.[a]
[a] Conditions: acetyl phosphonate 1, 2, or 3 (10.0 mmol), ArSO2Cl (15.0 mmol), DBU (15.0 mmol), CH3CN, 0 °C to room temp., overnight, isolated yield.
Eur. J. Org. Chem. 2016, 1577–1587 www.eurjoc.org © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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cantly alter the reaction outcome (Table 2). For example, aryl- phenylboronic acid 8a, phenylboronic esters, such as phenyl-
sulfonates with electron-donating groups (methyl, methoxy, boronic acid pinacol ester 12, phenylboronic acid neopentyl-
and tert-butyl; Table 2, Entries 2–4) and electron-withdrawing
Table 4. Cross-coupling reaction of 6b with various arylboronic acids.[a]
groups (fluorine and nitro; Table 2, Entries 5 and 6) at the para
position produced desired product 10a in 90–99 % yields. We
assumed that 6g and 6h (Table 2, Entries 7 and 8) were
more interesting because the relief of the steric bulk could be
favorable to the oxidative-addition step in the catalytic reac-
tions.[29] However, the steric effect on the phenyl ring was negli-
gible (Table 2, Entry 1 versus 7 and 8). Furthermore, dimethyl
and diisopropyl α-phenyl vinylphosphonates could be accessed
efficiently under the same reaction conditions (Table 2, Entries 9
and 10).
Entry
Ar
Product
Yield [%]
1
2
3
4
5
6
7
2-MeC6H4
3-MeC6H4
4-MeC6H4
10b
10c
10d
10e
10f
10g
10h
10i
10j
10k
10l
10m
10n
10o
10p
10q
10r
99
96
99
92
95
91
95
90
99
98
78
99
99
98
96
82
94
60
2-MeOC6H4
3-MeOC6H4
4-MeOC6H4
3,5-Me2C6H3
3,4-(MeO)2C6H3
3,4,5-(MeO)3C6H2
3,4-(OCH2O)C6H3
4-HOC6H4
4-(C2H3)C6H4
2-ClC6H4
3-ClC6H4
4-ClC6H4
3-BrC6H4
Table 2. Scope of α-phosphonovinyl arylsulfonates in Pd-catalyzed Suzuki
arylation reaction.
8[b]
9[b]
10[b]
11[b]
12[b]
13
14
15
Entry
Arylsulfonate
Product
Yield [%][a]
16[b]
17
4-FC6H4
4-CNC6H4
1
2
3
4
5
6
7
8
9
6a
6b
6c
6d
6e
6f
6g
6h
5
10a
10a
10a
10a
10a
10a
10a
10a
9
94
99
95
99
92
90
99
97
98
96
18[b,c]
19[b]
20[b]
21[b]
22
10s
10t
4-NO2C6H4
4-MeO2CC6H4
4-Me(O)CC6H4
4-PhC6H4
1-naphthyl
2-naphthyl
6-MeO-2-naphthyl
2,6-Me2C6H3
2,6-(MeO)2C6H3
2,4,6-Me3C6H2
60 (72[d]
92
)
10u
10v
10w
10x
10y
10z
10aa′
10ab′
10ac′
91
99
96
97
99
96
92
95
23
24
25[b]
26[b]
27[b]
28[b]
10
7
11
[a] Isolated yield.
[a] Reaction conditions: 6b (0.3 mmol), arylboronic acid 8 (0.6 mmol),
Pd(OAc)2 (7.0 mol-%), SPhos (15.0 mol-%), Cs2CO3 (2.5 equiv.), toluene, room
temperature, 15–20 h, isolated yield. [b] The reaction was carried out at 60 °C.
[c] XPhos (15 mol-%) was employed as the supporting ligand. [d] Compound
6a was used as the electrophilic coupling partner. XPhos: 2-dicyclohexylphos-
phino-2′,4′,6′-triisopropylbiphenyl.
In the view of high reactivity, easy preparation, operational
simplicity, and good economy, we selected crystalline 6b as the
model electrophile for further investigation. We next turned our
attention to the scope of the organoboron coupling partners
and the results were summarized in Table 3. In addition to
Table 3. Organoboron compatibility.
Entry
Organoboron reagent
Temperature [°C]
Yield [%][a]
1
2
12
13
14
15
60
60
60
94
97
90
99
3
4[b]
room temp.
[a] Isolated yield. [b] Toluene/H2O, 4:1, 0.15
M.
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glycol ester 13, and phenyl N-methyliminodiacetic acid boron- electron-withdrawing groups on the phenyl ring (nitrile, nitro,
ate 14,[30] could be employed as efficient coupling partners, ketone, and ester) participated in the reaction to deliver excel-
albeit at a higher reaction temperature (60 °C). It is worth not- lent product yields (Table 4, Entries 18–21), which highlights
ing that 6b could survive in aqueous conditions. By using tolu- the good functional group tolerance of this method. In addition
ene/H2O (4:1) as the solvent, potassium phenyltrifluoroborate to the above arylboronic acids, biphenyl and naphthylboronic
15[31] also participated in the reaction to afford desired product acids also reacted smoothly (Table 4, Entries 22–25). Of particu-
10a in 99 % yield. In terms of the atom-economy and ready lar note, sterically hindered di-ortho-substituted arylboronic
availability, arylboronic acids were chosen as the nucleophilic acids provided as high a yield as the less-hindered mono-substi-
coupling partners for the investigation of the substrate scope.
tuted nucleophiles (Table 4, Entries 26–28 versus 1 and 4).
To further challenge the applicability of our methodology,
We next turned to the scope of arylboronic acid 8 used for
the Suzuki arylation reaction. As shown in Table 4, electron- we examined the cross-coupling of 6b with a large variety of
neutral, -rich, and -deficient arylboronic acids were suitable heteroarylboron reagents, which included thiophenes, pyrid-
coupling partners in the present Suzuki arylation reactions. The ines, furan, benzofurans, indole, and quinoline (Table 5).[32] Gen-
reactions of tolyboronic acids with an electron-donating methyl erally, S-containing heterocyclic coupling partners are superior
group on the phenyl ring proceeded efficiently to afford corre- to O- and N-containing heteroarylborons. Of the four sulfur het-
sponding α-tolyl vinylphosphonates 10b–10d in excellent erocyclic boronic acids investigated reaction of thiophene-2-
yields regardless of the position of the methyl substituent boronic acid with 6b produced a somewhat lower product yield
(Table 4, Entries 1–3). This phenomenon was further witnessed (70 %). Interestingly, the yield could be improved by employing
by the couplings of methoxyphenylboronic acids (Table 4, En- potassium 2-thienyltrifluoroborate as the coupling partner. In
tries 4–6) and chlorophenylboronic acids (Table 4, Entries 13– addition, this method is effective for oxygen heteroarylborons
15). Interestingly, a hydroxyl group also affords the product in (e.g., 2-furan, 3-furan, 2-benzofuran, and 2-dibenzofuran). As for
a reasonable yield of 78 % (Table 4, Entry 11). In addition, an the coupling reaction of 6b and potassium benzofuran-2-yltri-
alkene was also tolerated (Table 4, Entry 12). Importantly, halo- fluoroborate, no better yields could be achieved by varying the
gen-substituted arylboronic acids could also be used as the source of Pd, ligand, or solvent. As a limitation of the present
coupling partners in this transformation (Table 4, Entries 13– method, 3- and 4-pyridineboronic acids or their corresponding
17). The halogen substituent on the benzene ring allows for pyridinetrifluoroborates were not suitable coupling partners.
further derivatization through transition-metal-catalyzed cross- Fortunately, application of the reaction conditions to potassium
coupling reactions. Impressively, arylboronic acids with strong N-methylindole-6-yltrifluoroborate afforded product 18i in 93 %
Table 5. Heteroarylboron reagents' scope.
[a] Heteroarylboronic acid 16 was used with toluene as solvent. [b] The use of potassium heteroaryltrifluoroborate 17 as the coupling partner with toluene/
H2O (4:1) as solvent. [c] Compound 6f was used in place of 6b. [d] Compound 6a was employed as the electrophilic coupling partner. [e] Compound 6e was
used.
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Table 6. Pd-catalyzed Suzuki alkylation reactions of 6b.
[a] Alkylboronic acid 19 was used in toluene. [b] By using potassium alkyltrifluoroborate 20 as the electrophile in toluene/H2O (4:1).
Scheme 2. Synthesis of estrone derivative 23.
yield. It is worth noting that the proper choice of electrophilic
To gauge the prospect for application to the complex syn-
coupling partners 6 is critical to the successful coupling of 8- thesis, estronylboronic acid 22a was selected as a representa-
quinolineboronic acid. With 6b as the electrophilic coupling tive coupling partner. Under the standard reaction conditions,
partner, desired product 18j could be achieved in 54 % yield. estrone derivative 23 was successfully prepared in 97 % yield,
After optimization, the yield of 18j could be increased to 90 % which highlights the good functional group tolerance and po-
with nitro-containing 6e as the electrophilic coupling partner.
Motivated by the successful (hetero)arylation of 6b, we in-
vestigated the Suzuki alkylation reaction.[33] To the best of our
knowledge, there are no examples for the synthesis of α-alkyl
vinylphosphonates by means of C–C cross-coupling reactions.
Consequently, we want to expand the scope of the coupling
reaction to the challenging alkylboron reagents. Gratifyingly,
alkylboronic acids 19 and alkyltrifluoroborates 20 reacted
tential application of this method. Moreover, we determined
that the Pd/SPhos-based method is effective for Suzuki cross-
coupling reactions of estronylboronic acid 22a, and for boron-
ate ester 22b, albeit at a higher temperature (Scheme 2).
Conclusions
smoothly with 6b to give desired products 21 in moderate to In summary, various α-phosphonovinyl arylsulfonates have
excellent yields. As indicated in Table 6, methylboronic acid been synthesized and the scope of the palladium-catalyzed
showed superior reactivity to corresponding potassium methyl- Suzuki cross-coupling reaction of these new O-centered electro-
trifluoroborate (46 versus 30 %). However, coupling of 6b and philes has been explored. We have demonstrated that easily
ethylboronic acid gave a poor result (13 %). To our delight, the accessible enol-derived arylsulfonates can serve as attractive
product yield of 21b could be increased to 42 % with potas- and efficient electrophilic coupling partners for the synthesis of
sium ethyltrifluoroborate as the nucleophile. Similar yields were α-substituted alkenylphosphonates. By using a catalyst com-
observed for coupling reaction of 6b and potassium propyltri- prised of Pd(OAc)2 and SPhos, a wide range of aryl, heteroaryl,
fluoroborate. The reactions of alkyltrifluoroborates with long and alkylboron reagents could be used to produce the corre-
chains all proceeded smoothly to give desired products 21d– sponding coupling products in moderate to excellent yields.
21g in excellent yields (21d: 87 %, 21e: 99 %, 21f: 98 %, 21g: The present method is characterized by a broad substrate
92 %). Furthermore, potassium cyclopropyltrifluoroborate also scope, mild reaction conditions, excellent functional group tol-
participated nicely and delivered product 21h in 98 % yield. erance, and high efficiency. We believe that our protocol will
Notably, α-cyclopropyl alkenylphosphonate 21h offers the op- be a powerful tool to provide α-substituted vinylphosphonates
portunity for further elaboration.
for various applications and transformations.
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(500 MHz, CDCl3): δ = 1.26 (t, J = 7.1 Hz, 6 H), 1.35 (s, 9 H), 3.92–
4.10 (m, 4 H), 5.98 (dd, J1 = 2.8, J2 = 6.5 Hz, 1 H), 6.03 (dd, J1 = 2.8,
J2 = 29.1 Hz, 1 H), 7.57 (d, J = 8.6 Hz, 2 H), 7.87 (d, J = 8.6 Hz, 2
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 16.1 (d, J = 6.3 Hz), 30.9,
35.3, 63.1 (d, J = 5.5 Hz), 119.2 (d, J = 23.3 Hz), 126.2, 128.3, 132.8,
145.8 (d, J = 226.5 Hz), 158.5 ppm. 31P NMR (202.5 MHz, CDCl3): δ =
Experimental Section
General Information: All reactions were carried out under an at-
mosphere of nitrogen in oven-dried glassware. Dichloromethane,
acetonitrile, and toluene were distilled from calcium hydride. All
organoboronic acids were obtained from commercial suppliers and
were used without further purification. Organotrifluoroborates,[34]
acetyl phosphonates 1–3,[35] and estrone derived arylboron rea-
gents 22[36] were synthesized in accordance with the reported pro-
cedure. NMR spectra were recorded in CDCl3 with a Bruker Avance
500 spectrometer with tetramethylsilane as an internal reference.
High-resolution mass spectra were recorded with a ESI-Q-TOF spec-
trometer (Bruker micrOTOF-Q II).
5.8 ppm. IR (KBr): ν = 3502, 2968, 1618, 1381, 1267, 1206, 1177,
˜
1022, 941, 777, 719 cm–1. GC–MS: m/z (%) = 377 (0.5) [M + H+], 286
(11), 271 (100), 243 (36), 215 (15), 197 (16), 181 (16), 133 (49), 81
(34). HRMS (ESI): calcd. for C16H25O6PSNa [M + Na]+ 399.1007; found
399.1013.
1-(Diethoxyphosphoryl)vinyl 4-Nitrobenzenesulfonate (6e): Yel-
1
low solid, 1.46 g, 40 % yield, m.p. 62.2–63.6 °C. H NMR (500 MHz,
General Procedure for the Synthesis of α-Phosphonovinyl Aryl-
sulfonate (5–7): To a dry two-necked round-bottomed flask with a
magnetic stir bar under a N2 atmosphere, diethyl acetyl phosphon-
ate (1.8 g, 10 mmol) and arylsulfonyl chloride (15 mmol) in CH3CN
(45 mL) was added. The reaction flask was cooled to 0 °C. Then,
DBU (2.2 mL, 15 mmol) was slowly added. At the end of this time,
the resulting mixture was allowed to stir at room temp. overnight.
Upon completion of the reaction, the resulting mixture was ex-
tracted with CH2Cl2 (3 × 15 mL). The combined organic phase was
dried with anhydrous MgSO4. After the removal of solvent under
reduced pressure, the crude product was purified by column chro-
matography with silica gel (petroleum/EtOAc, 2:1, v/v) to afford α-
phosphonovinyl arylsulfonate.
CDCl3): δ = 1.28 (t, J = 7.1 Hz, 6 H), 4.00–4.13 (m, 4 H), 6.03 (dd, J1 =
3.1, J2 = 9.2 Hz, 1 H), 6.07 (dd, J1 = 3.1, J2 = 14.3 Hz, 1 H), 8.18 (d,
J = 8.7 Hz, 2 H), 8.41 (d, J = 8.7 Hz, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 16.1 (d, J = 6.2 Hz), 63.3 (d, J = 5.6 Hz), 120.6 (d, J =
22.8 Hz), 124.3, 129.8, 141.4, 145.8 (d, J = 228.0 Hz), 151.0 ppm. 31P
NMR (202.5 MHz, CDCl3): δ = 5.0 ppm. IR (KBr): ν = 3446, 2990,
˜
1543, 1386, 1262, 1198, 1170, 1044, 1019, 945, 751 cm–1. GC–MS:
m/z (%) = 366 (0.1) [M + H+], 310 (8), 259 (5), 203 (17), 123 (25),
109 (100), 81 (53). HRMS (ESI): calcd. for C12H16NO8PSNa [M + Na]+
388.0232; found 388.0235.
1-(Diethoxyphosphoryl)vinyl 4-Fluorobenzenesulfonate (6f):
Pale yellow oil, 2.33 g, 69 % yield. 1H NMR (500 MHz, CDCl3): δ =
1.28 (t, J = 7.1 Hz, 6 H), 3.98–4.14 (m, 4 H), 5.98–6.00 (m, 1 H), 6.04
(dd, J1 = 2.9, J2 = 20.0 Hz, 1 H), 7.23–7.27 (m, 2 H), 7.98–8.01 (m, 2
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 16.1 (d, J = 6.0 Hz), 63.2 (d,
J = 5.6 Hz), 116.5 (d, J = 22.7 Hz), 119.7 (d, J = 23.1 Hz), 131.3 (d,
J = 9.7 Hz), 131.9 (d, J = 3.0 Hz), 145.9 (d, J = 226.9 Hz), 166.1 (d,
J = 256.3 Hz) ppm. 31P NMR (202.5 MHz, CDCl3): δ = 5.5 ppm. 19F
1-(Dimethoxyphosphoryl)vinyl
4-Methylbenzenesulfonate
(5):[26a] White solid, 2.45 g, 80 % yield, m.p. 38.2–40.4 °C. 1H NMR
(500 MHz, CDCl3): δ = 2.46 (s, 3 H), 3.66 (d, J = 11.3 Hz, 6 H), 6.00
(dd, J1 = 2.9, J2 = 6.8 Hz, 1 H), 6.04 (dd, J1 = 2.9, J2 = 17.6 Hz, 1 H),
7.37 (d, J = 8.1 Hz, 2 H), 7.84 (d, J = 8.4 Hz, 2 H) ppm.
1-(Diethoxyphosphoryl)vinyl Benzenesulfonate (6a): Pale yellow
oil, 2.82 g, 88 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.27 (t, J =
7.1 Hz, 6 H), 3.95–4.11 (m, 4 H), 5.97 (dd, J1 = 2.9, J2 = 6.5 Hz, 1 H),
6.02 (dd, J1 = 2.9, J2 = 17.4 Hz, 1 H), 7.56–7.59 (m, 2 H), 7.68–7.71
(m, 1 H), 7.96–7.80 (m, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
16.1 (d, J = 6.2 Hz), 63.2 (d, J = 5.5 Hz), 119.5 (d, J = 23.3 Hz), 128.4,
129.2, 134.4, 135.9, 145.9 (d, J = 226.7 Hz) ppm. 31P NMR
NMR (470 MHz, CDCl3): δ = –101.7 ppm. IR (KBr): ν = 3482, 2988,
˜
1593, 1445, 1385, 1266, 1199, 1021, 941, 777, 729 cm–1. GC–MS: m/z
(%) = 339 (2) [M + H+], 283 (8), 248 (13), 176 (20), 159 (46), 109
(100), 95 (94), 81 (50). HRMS (ESI): calcd. for C12H16FO6PSNa [M +
Na]+ 361.0287; found 361.0282.
1-(Diethoxyphosphoryl)vinyl 2,4,6-Trimethylbenzenesulfonate
1
(6g):[26a] White solid, 3.04 g, 84 % yield, m.p. 54.3–57.5 °C. H NMR
(202.5 MHz, CDCl3): δ = 5.6 ppm. IR (KBr): ν = 3502, 2987, 1619,
˜
1450, 1381, 1265, 1200, 1176, 1021, 941, 778 cm–1. GC–MS: m/z
(%) = 321 (3) [M + H+], 265 (8), 174 (45), 158 (10), 141 (30), 124 (49),
109 (62), 77 (100). HRMS (ESI): calcd. for C12H17O6PSNa [M + Na]+
343.0381; found 343.0374.
(500 MHz, CDCl3): δ = 1.29 (t, J = 7.1 Hz, 6 H), 2.32 (s, 3 H), 2.65 (s,
6 H), 3.97–4.13 (m, 4 H), 5.81 (dd, J1 = 2.7, J2 = 34.6 Hz, 1 H), 5.94
(dd, J1 = 2.8, J2 = 11.4 Hz, 1 H), 6.99 (s, 2 H) ppm.
1-(Diethoxyphosphoryl)vinyl 2,4,6-Triisopropylbenzenesulfon-
1
1-(Diethoxyphosphoryl)vinyl
4-Methylbenzenesulfonate
ate (6h): White solid, 2.90 g, 65 % yield, m.p. 74.3–76.2 °C. H NMR
(6b):[5a] White solid, 2.91 g, 87 % yield. 1H NMR (500 MHz, CDCl3):
δ = 1.28 (td, J1 = 0.5, J2 = 7.1 Hz, 6 H), 2.45 (s, 3 H), 3.95–4.12 (m, 4
H), 5.94–5.96 (m, 1 H), 5.97–6.01 (m, 1 H), 7.36 (d, J = 7.9 Hz, 2 H),
7.83 (d, J = 8.1 Hz, 2 H) ppm.
(500 MHz, CDCl3): δ = 1.25–1.31 (m, 24 H), 2.88–2.96 (m, 1 H), 4.03–
4.16 (m, 6 H), 5.75 (dd, J1 = 2.7, J2 = 34.6 Hz, 1 H), 6.00 (dd, J1 = 2.7,
J2 = 11.3 Hz, 1 H), 7.21 (s, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
16.1 (d, J = 6.5 Hz), 23.5, 24.6, 29.8, 34.3, 63.1 (d, J = 5.4 Hz), 119.5
(d, J = 23.7 Hz), 123.9, 130.8, 145.9 (d, J = 225.0 Hz), 150.8,
1-(Diethoxyphosphoryl)vinyl 4-Methoxybenzenesulfonate (6c):
Pale yellow oil, 3.12 g, 89 % yield. 1H NMR (500 MHz, CDCl3): δ =
1.28 (t, J = 7.1 Hz, 6 H), 3.89 (s, 3 H), 3.96–4.12 (m, 4 H), 5.95 (s, 1
H), 5.99 (dd, J1 = 2.8, J2 = 22.1 Hz, 1 H), 6.99–7.02 (m, 2 H), 7.86–
7.89 (m, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 16.1 (d, J =
6.3 Hz), 55.7, 63.2 (d, J = 5.5 Hz), 114.3, 119.1 (d, J = 23.3 Hz), 127.2,
130.7, 145.9 (d, J = 226.5 Hz), 164.3 ppm. 31P NMR (202.5 MHz,
154.4 ppm. 31P NMR (202.5 MHz, CDCl3): δ = 6.1 ppm. IR (KBr): ν =
˜
3438, 2961, 1620, 1388, 1264, 1203, 1173, 1024, 947, 723 cm–1. GC–
MS: m/z (%) = 447 (0.1) [M + H+], 361 (14), 305 (10), 267 (62), 251
(28), 203 (100), 175 (46), 81 (23). HRMS (ESI): calcd. for C21H35O6PSNa
[M + Na]+ 469.1790; found 469.1804.
1-(Diisopropoxyphosphoryl)vinyl
4-Methylbenzenesulfonate
CDCl3): δ = 5.8 ppm. IR (KBr): ν = 3487, 2986, 1596, 1501, 1362,
(7): White solid, 2.03 g, 56 % yield, m.p. 59.8–60.7 °C. 1H NMR
(500 MHz, CDCl3): δ = 1.27 (dd, J1 = 6.2, J2 = 24.3 Hz, 12 H), 2.46 (s,
3 H), 4.59–4.68 (m, 2 H), 5.91 (dd, J1 = 2.9, J2 = 6.4 Hz, 1 H), 5.96
(dd, J1 = 2.9, J2 = 28.8 Hz, 1 H), 7.35 (d, J = 8.3 Hz, 2 H), 7.84 (d, J =
8.3 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 21.7, 23.7 (dd,
J1 = 4.1, J2 = 39.6 Hz), 72.3 (d, J = 5.9 Hz), 117.2 (d, J = 22.6 Hz),
128.4, 129.8, 133.1, 145.5, 147.2 (d, J = 228.5 Hz) ppm. 31P NMR
˜
1266, 1201, 1170, 1022, 940, 808, 728 cm–1. GC–MS: m/z (%) = 350
(2) [M+], 260 (59), 216 (37), 188 (37), 171 (89), 155 (55), 107 (100),
92 (55), 77 (83). HRMS (ESI): calcd. for C13H19O7PSNa [M + Na]+
373.0487; found 373.0499.
1-(Diethoxyphosphoryl)vinyl
4-(tert-Butyl)benzenesulfonate
(6d): White solid, 3.20 g, 85 % yield, m.p. 46.4–47.8 °C. 1H NMR
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Full Paper
(202.5 MHz, CDCl3): δ = 3.4 ppm. IR (KBr): ν = 3425, 2982, 2953, (t, J = 7.1 Hz, 6 H), 3.80 (s, 3 H), 4.08 (m, 4 H), 6.04 (dd, J1 = 1.9, J2 =
˜
1619, 1374, 1354, 1257, 1184, 1170, 1093, 984, 938, 784 cm–1. GC– 46.9 Hz, 1 H), 6.44 (dd, J1 = 1.9, J2 = 22.2 Hz, 1 H), 6.90–6.95 (m, 2
MS: m/z (%) = 363 (0.1) [M + H+], 278 (20), 261 (20), 188 (50), 155 H), 7.25–7.30 (m, 2 H) ppm.
(61), 123 (47), 91 (100), 65 (29). HRMS (ESI): calcd. for C15H23O6PSNa
Diethyl [1-(3-Methoxyphenyl)vinyl]phosphonate (10f):[2c] Pale
yellow oil, 76.9 mg, 95 % yield. H NMR (500 MHz, CDCl3): δ = 1.29
[M + Na]+ 385.0851; found 385.0837.
1
General Procedure A: Synthesis of α-Substituted Vinylphos-
phonates 9, 10, 11, 18a–18d, 18f, 18h, 18j, 21a–21b, and 23
with Organoboronic Acids as the Coupling Partner: A Schlenk
flask was loaded with α-phosphonovinyl arylsulfonate (0.3 mmol),
Pd(OAc)2 (4.7 mg, 0.021 mmol), SPhos (18.5 mg, 0.045 mmol), or-
ganoboronic acid (0.6 mmol), Cs2CO3 (244.5 mg, 0.75 mmol) and
held under vacuum for 10 min and then filled with nitrogen. Then
toluene (2.0 mL) was introduced and the mixture was stirred at
room temp. or 60 °C for 15–20 h. After completion of the reaction,
the mixture was cooled to room temperature and diluted with
EtOAc (15.0 mL). The catalyst and inorganic base were separated by
filtration through a short pad of silica gel. The filtrate was concen-
trated under reduced pressure. The residue was purified by column
chromatography with silica gel (petroleum ether/EtOAc, 2:1, v/v) to
give α-substituted vinylphosphonate.
(t, J = 7.1 Hz, 6 H), 3.82 (s, 3 H), 4.11 (m, 4 H), 6.16 (dd, J1 = 1.6, J2 =
45.6 Hz, 1 H), 6.33 (dd, J1 = 1.6, J2 = 21.9 Hz, 1 H), 6.87–6.89 (m, 1
H), 7.09–7.12 (m, 2 H), 7.25–7.28 (m, 1 H) ppm.
Diethyl [1-(4-Methoxyphenyl)vinyl]phosphonate (10g):[1a] Pale
1
yellow oil, 73.7 mg, 91 % yield. H NMR (500 MHz, CDCl3): δ = 1.28
(t, J = 7.1 Hz, 6 H), 3.82 (s, 3 H), 4.03–4.17 (m, 4 H), 6.10 (dd, J1
=
1.5, J2 = 46.0 Hz, 1 H), 6.25 (dd, J1 = 1.5, J2 = 21.9 Hz, 1 H), 6.88 (m,
2 H), 7.48 (m, 2 H) ppm.
Diethyl [1-(3,5-Dimethylphenyl)vinyl]phosphonate (10h):[26a]
1
Pale yellow oil, 76.4 mg, 95 % yield. H NMR (500 MHz, CDCl3): δ =
1.30 (t, J = 7.1 Hz, 6 H), 2.32 (s, 6 H), 4.04–4.17 (m, 4 H), 6.12 (dd,
J1 = 1.6, J2 = 45.9 Hz, 1 H), 6.28 (dd, J1 = 1.6, J2 = 22.0 Hz, 1 H), 6.97
(s, 1 H), 7.13 (s, 2 H) ppm.
Diethyl [1-(3,4-Dimethoxyphenyl)vinyl]phosphonate (10i):[1a]
1
General Procedure B: Synthesis of α-Substituted Vinylphos-
phonates 10a, 18b, 18e, 18g, 18i and 21b–21h with Potassium
Trifluoroborates as the Coupling Partner: A Schlenk flask was
loaded with α-phosphonovinyl arylsulfonate (0.3 mmol), Pd(OAc)2
(4.7 mg, 0.021 mmol), SPhos (18.5 mg, 0.045 mmol), potassium tri-
fluoroborate (0.6 mmol), Cs2CO3 (244.5 mg, 0.75 mmol) and held
under vacuum for 10 min and then filled with nitrogen. Then tolu-
ene/water (4:1, v/v, 2.0 mL) was introduced and the mixture was
stirred at room temp. or 60 °C for 15–20 h. Upon completion of the
reaction, the resulting mixture was cooled to room temperature
and extracted with EtOAc (3 × 5 mL). The combined organic phase
was dried with anhydrous MgSO4. After the removal of solvent un-
der reduced pressure, the crude product was purified by column
chromatography with silica gel (petroleum ether/EtOAc, 2:1, v/v) to
give α-substituted vinylphosphonate.
Pale yellow oil, 81.0 mg, 90 % yield. H NMR (500 MHz, CDCl3): δ =
1.30 (t, J = 7.1 Hz, 6 H), 3.89 (s, 3 H), 3.90 (s, 3 H), 4.06–4.16 (m, 4
H), 6.11 (dd, J1 = 1.3, J2 = 45.7 Hz, 1 H), 6.36 (dd, J1 = 1.1, J2
21.9 Hz, 1 H), 6.85 (d, J = 8.3 Hz, 1 H), 7.12 (m, 2 H) ppm.
=
Diethyl [1-(3,4,5-Trimethoxyphenyl)vinyl]phosphonate (10j):[26c]
1
Pale yellow oil, 98.0 mg, 99 % yield. H NMR (500 MHz, CDCl3): δ =
1.31 (t, J = 7.1 Hz, 6 H), 3.86 (s, 3 H), 3.87 (s, 6 H), 4.07–4.18 (m, 4
H), 6.13 (dd, J1 = 1.4, J2 = 45.5 Hz, 1 H), 6.28 (dd, J1 = 1.4, J2
21.7 Hz, 1 H), 6.80 (d, J = 1.1 Hz, 2 H) ppm.
=
Diethyl
[1-(Benzo[d][1,3]dioxol-5-yl)vinyl]phosphonate
(10k):[26c] Pale yellow oil, 83.5 mg, 98 % yield. 1H NMR (500 MHz,
CDCl3): δ = 1.30 (t, J = 7.1 Hz, 6 H), 4.04–4.17 (m, 4 H), 5.97 (s, 2 H),
6.08 (dd, J1 = 1.4, J2 = 45.6 Hz, 1 H), 6.25 (dd, J1 = 1.4, J2 = 21.7 Hz,
1 H), 6.79 (dd, J1 = 0.5, J2 = 8.5 Hz, 1 H), 7.03–7.05 (m, 2 H) ppm.
Diethyl [1-(4-Hydroxyphenyl)vinyl]phosphonate (10l):[1a] Pale
yellow oil, 59.9 mg, 78 % yield. H NMR (500 MHz, CDCl3): δ = 1.30
Dimethyl (1-Phenylvinyl)phosphonate (9):[2c] Pale yellow oil,
1
62.3 mg, 98 % yield. 1H NMR (500 MHz, CDCl3): δ = 3.75 (dd, J1
=
(t, J = 7.1 Hz, 6 H), 4.11 (m, 4 H), 6.07 (dd, J1 = 1.2, J2 = 46.5 Hz, 1
H), 6.17 (dd, J1 = 1.2, J2 = 22.0 Hz, 1 H), 6.78 (m, 2 H), 7.35 (m, 2 H),
7.79 (br. s, 1 H) ppm.
0.7, J2 = 11.1 Hz, 6 H), 6.20 (d, J = 46.2 Hz, 1 H), 6.35 (d, J = 22.1 Hz,
1 H), 7.35 (m, 3 H), 7.50 (m, 2 H) ppm.
Diethyl (1-Phenylvinyl)phosphonate (10a):[2c] Pale yellow oil,
71.3 mg, 99 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.28 (t, J =
7.1 Hz, 6 H), 4.04–4.17 (m, 4 H), 6.16 (dd, J1 = 1.4, J2 = 45.8 Hz, 1
H), 6.33 (dd, J1 = 1.4, J2 = 22.0 Hz, 1 H), 7.31–7.37 (m, 3 H), 7.52–
7.53 (m, 2 H) ppm.
Diethyl [1-(o-Tolyl)vinyl]phosphonate (10b):[26a] Pale yellow oil,
75.4 mg, 99 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.27 (t, J =
7.0 Hz, 6 H), 2.31 (s, 3 H), 4.04–4.10 (m, 4 H), 5.84 (dd, J1 = 2.0, J2 =
47.7 Hz, 1 H), 6.42 (dd, J1 = 2.0, J2 = 22.6 Hz, 1 H), 7.13–7.17 (m, 2
H), 7.20–7.21 (m, 2 H) ppm.
Diethyl [1-(m-Tolyl)vinyl]phosphonate (10c):[26a] Pale yellow oil,
73.2 mg, 96 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.29 (t, J =
7.1 Hz, 6 H), 2.36 (s, 3 H), 4.05–4.16 (m, 4 H), 6.14 (dd, J1 = 1.5, J2 =
45.8 Hz, 1 H), 6.31 (dd, J1 = 1.5, J2 = 22.0 Hz, 1 H), 7.14 (d, J = 7.6 Hz,
1 H), 7.24 (t, J = 7.8 Hz, 1 H), 7.32–7.33 (m, 2 H) ppm.
Diethyl [1-(p-Tolyl)vinyl]phosphonate (10d):[2c] Pale yellow oil,
75.4 mg, 99 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.28 (t, J =
7.1 Hz, 6 H), 2.35 (s, 3 H), 4.03–4.17 (m, 4 H), 6.14 (dd, J1 = 1.6, J2 =
46.0 Hz, 1 H), 6.29 (dd, J1 = 1.6, J2 = 22.0 Hz, 1 H), 7.16 (d, J = 7.9 Hz,
2 H), 7.42 (m, 2 H) ppm.
Diethyl [1-(4-Vinylphenyl)vinyl]phosphonate (10m):[26c] Pale yel-
1
low oil, 79.0 mg, 99 % yield. H NMR (500 MHz, CDCl3): δ = 1.28 (t,
J = 7.1 Hz, 6 H), 4.03–4.17 (m, 4 H), 5.27 (d, J = 10.9 Hz, 1 H), 5.77
(d, J = 17.6 Hz, 1 H), 6.17 (dd, J1 = 1.4, J2 = 45.7 Hz, 1 H), 6.32 (dd,
J1 = 1.4, J2 = 22.0 Hz, 1 H), 6.71 (dd, J1 = 10.9, J2 = 17.6 Hz, 1 H),
7.39 (d, J = 8.1 Hz, 2 H), 7.50 (d, J = 8.2 Hz, 2 H) ppm.
Diethyl [1-(2-Chlorophenyl)vinyl]phosphonate (10n):[26a] Pale
1
yellow oil, 81.4 mg, 99 % yield. H NMR (500 MHz, CDCl3): δ = 1.28
(t, J = 7.1 Hz, 6 H), 4.07–4.13 (m, 4 H), 6.02 (dd, J1 = 0.8, J2 = 46.5 Hz,
1 H), 6.55 (dd, J1 = 0.8, J2 = 22.4 Hz, 1 H), 7.24 (t, J = 5.3 Hz, 2 H),
7.35–7.36 (m, 1 H), 7.40–7.42 (m, 1 H) ppm.
Diethyl [1-(3-Chlorophenyl)vinyl]phosphonate (10o):[1a] Pale yel-
1
low oil, 80.6 mg, 98 % yield. H NMR (500 MHz, CDCl3): δ = 1.30 (t,
J = 7.1 Hz, 6 H), 4.05–4.18 (m, 4 H), 6.16 (dd, J1 = 1.2, J2 = 45.2 Hz,
1 H), 6.36 (dd, J1 = 1.2, J2 = 21.8 Hz, 1 H), 7.24–7.32 (m, 2 H), 7.42–
7.43 (m, 1 H), 7.50 (d, J = 1.4 Hz, 1 H) ppm.
Diethyl [1-(4-Chlorophenyl)vinyl]phosphonate (10p):[1a] Pale yel-
1
low oil, 78.9 mg, 96 % yield. H NMR (500 MHz, CDCl3): δ = 1.29 (t,
J = 7.1 Hz, 6 H), 4.03–4.17 (m, 4 H), 6.14 (dd, J1 = 1.1, J2 = 45.4 Hz,
1 H), 6.32 (dd, J1 = 0.9, J2 = 21.9 Hz, 1 H), 7.32 (d, J = 8.4 Hz, 2 H),
7.46–7.47 (m, 2 H) ppm.
Diethyl [1-(2-Methoxyphenyl)vinyl]phosphonate (10e):[2c] Pale
1
yellow oil, 74.5 mg, 92 % yield. H NMR (500 MHz, CDCl3): δ = 1.27
Eur. J. Org. Chem. 2016, 1577–1587
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Diethyl [1-(3-Bromophenyl)vinyl]phosphonate (10q):[1a] Pale yel-
low oil, 78.2 mg, 82 % yield. H NMR (500 MHz, CDCl3): δ = 1.30 (t,
J = 7.1 Hz, 6 H), 4.05–4.19 (m, 4 H), 6.15 (d, J = 45.2 Hz, 1 H), 6.35
(d, J = 21.9 Hz, 1 H), 7.22 (t, J = 7.9 Hz, 1 H), 7.45–7.48 (m, 2 H), 7.65
(s, 1 H) ppm.
CDCl3): δ = 1.29 (t, J = 7.1 Hz, 6 H), 3.93 (s, 3 H), 4.06–4.20 (m, 4 H),
6.27 (dd, J1 = 1.3, J2 = 45.8 Hz, 1 H), 6.38 (dd, J1 = 1.3, J2 = 21.9 Hz,
1 H), 7.12–7.17 (m, 2 H), 7.61 (d, J = 8.6 Hz, 1 H), 7.71–7.76 (m, 2 H),
7.97 (s, 1 H) ppm.
1
Diethyl [1-(2,6-Dimethylphenyl)vinyl]phosphonate (10aa′): Pale
Diethyl [1-(4-Fluorophenyl)vinyl]phosphonate (10r):[2c] Pale yel-
1
yellow oil, 77.2 mg, 96 % yield. H NMR (500 MHz, CDCl3): δ = 1.26
1
low oil, 72.8 mg, 94 % yield. H NMR (500 MHz, CDCl3): δ = 1.28 (t,
(t, J = 7.1 Hz, 6 H), 2.28 (s, 6 H), 4.00–4.11 (m, 4 H), 5.77 (dd, J1
=
J = 7.1 Hz, 6 H), 4.04–4.17 (m, 4 H), 6.16 (dd, J1 = 1.5, J2 = 45.8 Hz,
1 H), 6.34 (dd, J1 = 1.5, J2 = 22.0 Hz, 1 H), 7.31–7.38 (m, 2 H), 7.51–
7.53 (m, 2 H) ppm.
2.0, J2 = 48.6 Hz, 1 H), 6.43 (dd, J1 = 2.0, J2 = 22.5 Hz, 1 H), 7.04 (d,
J = 7.5 Hz, 2 H), 7.09–7.12 (m, 1 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 16.3 (d, J = 6.3 Hz), 20.4, 62.2 (d, J = 6.5 Hz), 127.4 (d, J = 1.3 Hz),
127.5 (d, J = 2.4 Hz), 132.5 (d, J = 8.2 Hz), 136.2 (d, J = 8.6 Hz), 136.6
(d, J = 4.4 Hz), 140.2 (d, J = 177.0 Hz) ppm. 31P NMR (202.5 MHz,
Diethyl [1-(4-Cyanophenyl)vinyl]phosphonate (10s):[26a] Pale yel-
1
low oil, 47.7 mg, 60 % yield. H NMR (500 MHz, CDCl3): δ = 1.29 (t,
CDCl ): δ = 15.9 ppm. IR (KBr): ν = 3482, 2982, 2906, 1473, 1391,
J = 7.1 Hz, 6 H), 4.07–4.17 (m, 4 H), 6.21 (dd, J1 = 1.1, J2 = 44.8 Hz,
1 H), 6.42 (dd, J1 = 1.1, J2 = 21.9 Hz, 1 H), 7.64 (s, 4 H) ppm.
˜
3
1245, 1222, 1022, 965 cm–1. GC–MS: m/z (%) = 268 (24) [M+], 240
(6), 211 (38), 177 (5), 129 (100), 115 (36), 91 (14), 77 (6). HRMS (ESI):
calcd. for C14H21O3PNa [M + Na]+ 291.1121; found 291.1124.
Diethyl [1-(4-Nitrophenyl)vinyl]phosphonate (10t): Yellow oil,
61.6 mg, 72 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.30 (t, J =
7.1 Hz, 6 H), 4.07–4.20 (m, 4 H), 6.25 (dd, J1 = 1.0, J2 = 44.7 Hz, 1
Diethyl [1-(2,6-Dimethoxyphenyl)vinyl]phosphonate (10ab′):[26c]
1
H), 6.46 (dd, J1 = 0.9, J2 = 21.9, Hz, 1 H), 7.70 (dd, J1 = 1.1, J2
=
Pale yellow oil, 82.8 mg, 92 % yield. H NMR (500 MHz, CDCl3): δ =
8.9 Hz, 2 H), 8.21 (d, J = 8.4 Hz, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 16.2 (d, J = 5.9 Hz), 62.6 (d, J = 5.7 Hz), 123.6, 128.4 (d,
J = 5.5 Hz), 133.8 (d, J = 7.1 Hz), 138.6 (d, J = 177.1 Hz), 143.2 (d,
J = 11.8 Hz), 147.6 ppm. 31P NMR (202.5 MHz, CDCl3): δ = 15.2 ppm.
1.25 (t, J = 7.1 Hz, 6 H), 3.77 (d, J = 1.5 Hz, 6 H), 4.05–4.10 (m, 4 H),
5.90 (dd, J1 = 1.4, J2 = 47.4 Hz, 1 H), 6.48 (dd, J1 = 1.4, J2 = 21.8 Hz,
1 H), 6.55 (d, J = 8.4 Hz, 2 H), 7.20–7.24 (m, 1 H) ppm.
Diethyl (1-Mesitylvinyl)phosphonate (10ac′):[26c] Pale yellow oil,
80.4 mg, 95 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.26 (t, J =
7.1 Hz, 6 H), 2.24 (s, 6 H), 2.26 (s, 3 H), 4.01–4.09 (m, 4 H), 5.74 (dd,
J1 = 1.9, J2 = 48.7 Hz, 1 H), 6.41 (dd, J1 = 1.9, J2 = 22.4 Hz, 1 H), 6.86
(s, 2 H) ppm.
IR (KBr): ν = 3481, 2985, 2907, 1595, 1522, 1347, 1234, 1019, 969 cm–
˜
1. GC–MS: m/z (%) = 285 (35) [M+], 257 (100), 240 (55), 213 (32), 166
(12), 149 (59), 102 (87), 91 (52). HRMS (ESI): calcd. for C12H16O5PNNa
[M + Na]+ 308.0658; found 308.0669.
Methyl 4-[1-(Diethoxyphosphoryl)vinyl]benzoate (10u):[26c] Pale
Diisopropyl (1-Phenylvinyl)phosphonate (11):[6a] Pale yellow oil,
77.2 mg, 96 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.19 (d, J =
6.2 Hz, 6 H), 1.32 (d, J = 6.2 Hz, 6 H), 4.64–4.73 (m, 2 H), 6.12 (dd,
J1 = 1.6, J2 = 45.7 Hz, 1 H), 6.33 (dd, J1 = 1.6, J2 = 22.0 Hz, 1 H),
7.29–7.35 (m, 3 H), 7.52–7.54 (m, 2 H) ppm.
1
yellow oil, 82.2 mg, 92 % yield. H NMR (500 MHz, CDCl3): δ = 1.28
(t, J = 7.1 Hz, 6 H), 3.92 (s, 3 H), 4.05–4.18 (m, 4 H), 6.22 (dd, J1
=
1.2, J2 = 45.2 Hz, 1 H), 6.41 (dd, J1 = 1.2, J2 = 22.0, Hz, 1 H), 7.59–
7.61 (m, 2 H), 8.0 (d, J = 8.1 Hz, 2 H) ppm.
Diethyl [1-(4-Acetylphenyl)vinyl]phosphonate (10v): Pale yellow
Diethyl [1-(Thiophen-3-yl)vinyl]phosphonate (18a):[26a] Pale yel-
1
oil, 77.0 mg, 91 % yield. H NMR (500 MHz, CDCl3): δ = 1.29 (t, J =
1
low oil, 65.7 mg, 89 % yield. H NMR (500 MHz, CDCl3): δ = 1.30 (t,
7.1 Hz, 6 H), 2.61 (s, 3 H), 4.06–4.19 (m, 4 H), 6.23 (dd, J1 = 1.3, J2 =
J = 7.1 Hz, 6 H), 4.06–4.17 (m, 4 H), 6.21 (dd, J1 = 1.3, J2 = 23.1 Hz,
1 H), 6.28 (s, 1 H), 7.29–7.30 (m, 2 H), 7.58 (m, 1 H) ppm.
45.2 Hz, 1 H), 6.41 (dd, J1 = 1.2, J2 = 22.0, Hz, 1 H), 7.63 (dd, J1
=
1.2, J2 = 8.5 Hz, 2 H), 7.95 (d, J = 8.1 Hz, 2 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 16.2 (d, J = 6.1 Hz), 26.5, 62.3 (d, J = 5.7 Hz),
127.6 (d, J = 5.5 Hz), 128.4, 132.9 (d, J = 7.4 Hz), 136.6, 139.2 (d, J =
175.2 Hz), 141.3 (d, J = 11.6 Hz), 197.5 ppm. 31P NMR (202.5 MHz,
Diethyl [1-(Thiophen-2-yl)vinyl]phosphonate (18b):[6a] Pale yel-
1
low oil, 65.7 mg, 89 % yield. H NMR (500 MHz, CDCl3): δ = 1.32 (t,
J = 7.1 Hz, 6 H), 4.06–4.21 (m, 4 H), 6.18 (d, J = 13.6 Hz, 1 H), 6.25
(d, J = 36.5 Hz, 1 H), 7.01 (dd, J1 = 3.7, J2 = 5.1 Hz, 1 H), 7.25 (m, 1
H), 7.36 (m, 1 H) ppm.
CDCl3): δ = 16.0 ppm. IR (KBr): ν = 3502, 2984, 2906, 1687, 1604,
˜
1404, 1361, 1262, 1232, 1016, 961 cm–1. GC–MS: m/z (%) = 282 (78)
[M+], 267 (78), 254 (33), 239 (100), 223 (16), 211 (71), 193 (97), 145
(62), 91 (51). HRMS (ESI): calcd. for C14H19O4PNa [M + Na]+ 305.0913;
found 305.0915.
Diethyl [1-(Benzo[b]thiophen-2-yl)vinyl]phosphonate (18c):[26c]
1
Pale yellow oil, 72.8 mg, 82 % yield. H NMR (500 MHz, CDCl3): δ =
1.33 (t, J = 7.1 Hz, 6 H), 4.08–4.23 (m, 4 H), 6.30 (d, J = 6.8 Hz, 1 H),
6.36 (d, J = 15.5 Hz, 1 H), 7.30–7.36 (m, 2 H), 7.64 (s, 1 H), 7.73–7.78
(m, 2 H) ppm.
Diethyl {1-[(1,1′-Biphenyl)-4-yl]vinyl}phosphonate (10w):[2b] Pale
1
yellow oil, 93.9 mg, 99 % yield. H NMR (500 MHz, CDCl3): δ = 1.31
(t, J = 7.1 Hz, 6 H), 4.09–4.19 (m, 4 H), 6.23 (dd, J1 = 1.4, J2 = 45.7 Hz,
1 H), 6.36 (dd, J1 = 1.4, J2 = 22.0 Hz, 1 H), 7.36 (m, 1 H), 7.45 (m, 2
H), 7.61 (m, 6 H) ppm.
Diethyl
[1-(Dibenzo[b,d]thiophen-4-yl)vinyl]phosphonate
(18d):[26c] Orange oil, 101.7 mg, 98 % yield. 1H NMR (500 MHz,
CDCl3): δ = 1.25 (t, J = 7.1 Hz, 6 H), 4.07–4.16 (m, 4 H), 6.48 (dd, J1 =
1.3, J2 = 46.3 Hz, 1 H), 6.69 (dd, J1 = 1.3, J2 = 22.3 Hz, 1 H), 7.45–
7.49 (m, 3 H), 7.58 (d, J = 7.5 Hz, 1 H), 7.83–7.85 (m, 1 H), 8.12 (d,
J = 7.9 Hz, 1 H), 8.15–8.16 (m, 1 H) ppm.
Diethyl [1-(Naphthalen-1-yl)vinyl]phosphonate (10x):[2c] Pale
1
yellow oil, 83.5 mg, 96 % yield. H NMR (500 MHz, CDCl3): δ = 1.19
(t, J = 7.1 Hz, 6 H), 3.99–4.10 (m, 4 H), 6.03 (dd, J1 = 2.0, J2 = 47.1 Hz,
1 H), 6.67 (dd, J1 = 2.0, J2 = 22.4 Hz, 1 H), 7.42–7.50 (m, 4 H), 7.81–
7.86 (m, 2 H), 8.01–8.02 (m, 1 H) ppm.
Diethyl [1-(Furan-2-yl)vinyl]phosphonate (18e):[37] Pale yellow
1
Diethyl [1-(Naphthalen-2-yl)vinyl]phosphonate (10y):[2b] Pale
oil, 56.6 mg, 82 % yield. H NMR (500 MHz, CDCl3): δ = 1.32 (t, J =
1
7.1 Hz, 6 H), 4.04–4.20 (m, 4 H), 6.14 (dd, J1 = 1.3, J2 = 22.5 Hz, 1
yellow oil, 84.4 mg, 97 % yield. H NMR (500 MHz, CDCl3): δ = 1.30
H), 6.40 (dd, J1 = 1.2, J2 = 44.4 Hz, 1 H), 6.41 (dd, J1 = 1.8, J2
3.3 Hz, 1 H), 6.65 (d, J = 3.3 Hz, 1 H), 7.40 (s, 1 H) ppm.
=
(t, J = 7.1 Hz, 6 H), 4.07–4.21 (m, 4 H), 6.29 (dd, J1 = 1.4, J2 = 45.6 Hz,
1 H), 6.43 (dd, J1 = 1.4, J2 = 21.9 Hz, 1 H), 7.45–7.51 (m, 2 H), 7.63–
7.66 (d, J = 8.5 Hz, 1 H), 7.82–7.87 (m, 3 H), 8.04 (s, 1 H) ppm.
Diethyl [1-(Furan-3-yl)vinyl]phosphonate (18f): Pale yellow oil,
68.3 mg, 99 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.32 (t, J =
7.1 Hz, 6 H), 4.03–4.18 (m, 4 H), 6.11 (d, J = 23.8 Hz, 1 H), 6.17 (s, 1
Diethyl
[1-(6-Methoxynaphthalen-2-yl)vinyl]phosphonate
(10z):[2c] Pale yellow oil, 95.0 mg, 99 % yield. 1H NMR (500 MHz,
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H), 6.57 (s, 1 H), 7.39 (d, J = 1.4 Hz, 1 H), 7.73 (s, 1 H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 16.3 (d, J = 6.3 Hz), 62.2 (d, J = 5.3 Hz), 108.1
(d, J = 9.7 Hz), 121.3 (d, J = 13.5 Hz), 128.1 (d, J = 7.2 Hz), 130.0 (d,
J = 176.8 Hz), 141.5 (d, J = 3.0 Hz), 143.2 ppm. 31P NMR (202.5 MHz,
216 (17), 169 (2), 154 (100), 127 (7), 77 (4). HRMS (ESI): calcd. for
C15H18O3PNNa [M + Na]+ 314.0917; found 314.0905.
Diethyl Prop-1-en-2-ylphosphonate (21a):[17a] Pale yellow oil,
24.6 mg, 46 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.33 (t, J =
7.1 Hz, 6 H), 1.94 (d, J = 14.0 Hz, 3 H), 4.04–4.13 (m, 4 H), 5.76 (dt,
J1 = 1.6, J2 = 48.3 Hz, 1 H) 5.97 (d, J = 22.3 Hz, 1 H) ppm.
CDCl3): δ = 16.9 ppm. IR (KBr): ν = 3528, 3114, 2984, 1393, 1250,
˜
1097, 1023, 963, 803 cm–1. GC–MS: m/z (%) = 230 (19) [M+], 186
(21), 173 (11), 158 (38), 120 (17), 111 (11), 94 (100), 81 (13), 65
(49). HRMS (ESI): calcd. for C10H15O4PNa [M + Na]+ 253.0600; found
253.0601.
Diethyl But-1-en-2-ylphosphonate (21b):[6a] Pale yellow oil,
24.2 mg, 42 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.12 (t, J =
7.4 Hz, 3 H), 1.32 (t, J = 7.1 Hz, 6 H), 2.24–2.31 (m, 2 H), 4.02–4.14
(m, 4 H), 5.76 (dd, J1 = 1.6, J2 = 49.0 Hz, 1 H) 6.03 (dd, J1 = 1.1, J2 =
23.1 Hz, 1 H) ppm.
Diethyl [1-(Benzofuran-2-yl)vinyl]phosphonate (18g): Pale yel-
1
low oil, 29.4 mg, 35 % yield. H NMR (500 MHz, CDCl3): δ = 1.35 (t,
J = 7.1 Hz, 6 H), 4.09–4.24 (m, 4 H), 6.36 (dd, J1 = 1.4, J2 = 22.2 Hz,
1 H), 6.70 (dd, J1 = 1.3, J2 = 43.8 Hz, 1 H), 7.05 (s, 1 H), 7.20–7.23
(m, 1 H), 7.29–7.32 (m, 1 H), 7.45 (d, J = 8.2 Hz, 1 H), 7.57 (d, J =
7.7 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 16.3 (d, J = 6.4 Hz),
62.5 (d, J = 5.1 Hz), 107.2, 111.0, 121.6, 123.0, 125.4, 128.7, 128.7 (d,
J = 181.5 Hz), 129.6 (d, J = 3.6 Hz), 151.2 (d, J = 26.4 Hz), 154.6 ppm.
Diethyl Pent-1-en-2-ylphosphonate (21c):[6a] Pale yellow oil
(29.1 mg, 47 % yield). 1H NMR (500 MHz, CDCl3): δ = 1.25 (t, J =
7.2 Hz, 3 H), 1.32 (t, J = 7.1 Hz, 6 H), 1.52–1.59 (m, 2 H), 2.19–2.25
(m, 2 H), 4.05–4.14 (m, 4 H), 5.75 (dq, J1 = 1.6, J2 = 49.1 Hz, 1 H),
6.03 (dd, J1 = 0.7, J2 = 23.1 Hz, 1 H) ppm.
31P NMR (202.5 MHz, CDCl3): δ = 14.8 ppm. IR (KBr): ν = 3481, 2982,
Diethyl Hex-1-en-2-ylphosphonate (21d):[16a] Pale yellow oil,
57.4 mg, 87 % yield. 1H NMR (500 MHz, CDCl3): δ = 0.91 (t, J =
7.3 Hz, 3 H), 1.32 (t, J = 7.1 Hz, 6 H), 1.34 (m, 2 H), 1.50 (m, 2 H),
2.23 (m, 2 H), 4.03–4.12 (m, 4 H), 5.75 (dd, J1 = 1.5, J2 = 49.1 Hz, 1
H) 6.02 (dd, J1 = 0.8, J2 = 23.1 Hz, 1 H) ppm.
˜
2907, 1682, 1477, 1462, 1250, 1164, 1019, 969 cm–1. GC–MS: m/z
(%) = 280 (35) [M+], 236 (32), 208 (100), 193 (6), 169 (6), 144 (53),
115 (52), 89 (12). HRMS (ESI): calcd. for C14H17O4PNa [M + Na]+
303.0757; found 303.0740.
Diethyl [1-(Dibenzo[b,d]furan-2-yl)vinyl]phosphonate (18h): Off-
white oil, 98.0 mg, 99 % yield. H NMR (500 MHz, CDCl3): δ = 1.28
Diethyl Dodec-1-en-2-ylphosphonate (21e): Off-white oil
(90.3 mg, 99 % yield). H NMR (500 MHz, CDCl3): δ = 0.86–0.89 (m,
1
1
(t, J = 7.1 Hz, 6 H), 4.10–4.21 (m, 4 H), 6.71 (dd, J1 = 1.5, J2 = 21.0 Hz,
1 H), 6.78 (d, J = 1.4 Hz, 1 H), 7.33–7.37 (m, 2 H), 7.45–7.49 (m, 1 H),
7.58 (d, J = 8.3 Hz, 1 H), 7.70 (d, J = 7.7 Hz, 1 H), 7.91 (d, J = 7.7 Hz,
1 H), 7.96 (d, J = 7.7 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
16.1 (d, J = 6.3 Hz), 62.2 (d, J = 5.5 Hz), 111.6, 120.3, 120.5, 120.9 (d,
J = 12.8 Hz), 122.5, 122.8, 123.9, 124.6, 127.2, 127.3 (d, J = 3.0 Hz),
133.8 (d, J = 176.4 Hz), 135.5 (d, J = 6.4 Hz), 153.4 (d, J = 9.1 Hz),
3 H), 1.26–1.34 (m, 20 H), 1.48–1.53 (m, 2 H), 2.20–2.26 (m, 2 H),
4.02–4.13 (m, 4 H), 5.75 (dd, J1 = 1.6, J2 = 49.1 Hz, 1 H), 6.02 (d, J =
23.1 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 14.0, 16.2 (d, J =
6.0 Hz), 22.6, 27.8 (d, J = 5.4 Hz), 29.1, 29.2, 29.3, 29.5 (d, J = 2.5 Hz),
31.8, 32.0, 32.1, 61.6 (d, J = 5.6 Hz), 128.7 (d, J = 9.4 Hz), 139.4 (d,
J = 169.7 Hz) ppm. 31P NMR (202.5 MHz, CDCl3): δ = 20.0 ppm. IR
(KBr): ν = 3374, 2925, 2854, 1466, 1392, 1248, 1054, 1027, 965,
˜
155.8 ppm. 31P NMR (202.5 MHz, CDCl3): δ = 16.4 ppm. IR (KBr): ν =
˜
796 cm–1. GC–MS: m/z (%) = 304 (4) [M+], 289 (8), 261 (12), 233 (16),
179 (100), 138 (68), 123 (51), 109 (50), 81 (80). HRMS (ESI): calcd. for
C16H33O3PNa [M + Na]+ 327.2060; found 327.2055.
3502, 2983, 2905, 1450, 1413, 1394, 1239, 1193, 1019, 965 cm–1
.
GC–MS: m/z (%) = 330 (45) [M+], 302 (10), 286 (25), 258 (22), 220
(46), 194 (100), 165 (82), 139 (18). HRMS (ESI): calcd. for C18H19O4PNa
[M + Na]+ 353.0913; found 353.0903.
Diethyl (3-Phenylprop-1-en-2-yl)phosphonate (21f):[9] Pale yel-
low oil (74.7 mg, 98 % yield). 1H NMR (500 MHz, CDCl3): δ = 1.26 (t,
J = 7.1 Hz, 6 H), 3.56 (d, J = 11.5 Hz, 2 H), 3.92–4.09 (m, 4 H), 5.58
(dd, J1 = 1.6, J2 = 47.8 Hz, 1 H), 6.11 (dd, J1 = 1.2, J2 = 22.3 Hz, 1 H),
7.18–7.24 (m, 3 H), 7.29–7.32 (m, 2 H) ppm.
Diethyl [1-(1-Methyl-1H-indol-5-yl)vinyl]phosphonate (18i): Pale
1
yellow oil, 81.7 mg, 93 % yield. H NMR (500 MHz, CDCl3): δ = 1.28
(t, J = 7.1 Hz, 6 H), 3.79 (s, 3 H), 4.04–4.18 (m, 4 H), 6.16 (dd, J1
=
1.5, J2 = 46.1 Hz, 1 H), 6.11 (dd, J1 = 1.4, J2 = 21.8 Hz, 1 H), 6.49 (d,
J = 3.0 Hz, 1 H), 7.06 (d, J = 3.1 Hz, 1 H), 7.29 (d, J = 8.6 Hz, 1 H),
7.42 (d, J = 8.6 Hz, 1 H), 7.81 (s, 1 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 16.2 (d, J = 6.3 Hz), 32.8, 62.0 (d, J = 5.5 Hz), 101.5,
109.0, 120.1 (d, J = 6.2 Hz), 121.2 (d, J = 6.0 Hz), 127.9 (d, J =
11.9 Hz), 128.4, 129.4, 130.2 (d, J = 8.8 Hz), 136.5, 140.3 (d, J =
171.0 Hz) ppm. 31P NMR (202.5 MHz, CDCl3): δ = 18.1 ppm. IR (KBr):
Diethyl (4-Phenylbut-1-en-2-yl)phosphonate (21g): Pale yellow
1
oil, 74.0 mg, 92 % yield. H NMR (500 MHz, CDCl3): δ = 1.33 (t, J =
7.1 Hz, 6 H), 2.53–2.59 (m, 2 H), 2.83–2.86 (m, 2 H), 4.03–4.15 (m, 4
H), 5.75 (dd, J1 = 1.3, J2 = 48.7 Hz, 1 H), 6.06 (d, J = 23.0 Hz, 1 H),
7.18–7.21 (m, 3 H), 7.26–7.30 (m, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 16.3 (d, J = 6.2 Hz), 33.9 (d, J = 10.5 Hz), 34.3 (d, J =
5.4 Hz), 61.7 (d, J = 5.8 Hz), 126.0, 128.3, 128.4, 129.5 (d, J = 9.4 Hz),
138.5 (d, J = 170.9 Hz), 141.1 ppm. 31P NMR (202.5 MHz, CDCl3): δ =
ν = 3522, 3097, 2981, 2905, 1615, 1514, 1489, 1334, 1248, 1020,
˜
961 cm–1. GC–MS: m/z (%) = 293 (37) [M+], 278 (3), 249 (14), 220
(8), 182 (18), 157 (100), 141 (19), 115 (37), 77 (6). HRMS (ESI): calcd.
for C15H20NO3PNa [M + Na]+ 316.1073; found 316.1078.
19.4 ppm. IR (KBr): ν = 3421, 2982, 2933, 1456, 1393, 1246, 1052,
˜
1023, 962 cm–1. GC–MS: m/z (%) = 268 (16) [M+], 239 (7), 211 (11),
177 (21), 149 (16), 137 (22), 130 (41), 91 (100). HRMS (ESI): calcd. for
C14H21O3PNa [M + Na]+ 291.1121; found 291.1121.
Diethyl [1-(Quinolin-8-yl)vinyl]phosphonate (18j): Pale yellow oil,
78.6 mg, 90 % yield. 1H NMR (500 MHz, CDCl3): δ = 1.21 (t, J =
7.1 Hz, 6 H), 4.11–4.16 (m, 4 H), 6.17 (dd, J1 = 1.9, J2 = 46.6 Hz, 1
H), 6.68 (dd, J1 = 1.9, J2 = 22.4 Hz, 1 H), 7.39–7.42 (m, 1 H), 7.53 (t,
Diethyl (1-Cyclopropylvinyl)phosphonate (21h): Pale yellow oil,
1
60.0 mg, 98 % yield. H NMR (500 MHz, CDCl3): δ = 0.56–0.60 (m, 2
J = 7.7 Hz, 1 H), 7.74–7.76 (m, 1 H), 7.79–7.81 (m, 1 H), 8.16 (dd, J1 = H), 0.78–0.82 (m, 2 H), 1.35 (t, J = 7.1 Hz, 6 H), 1.53–1.60 (m, 1 H),
1.8, J2 = 8.3 Hz, 1 H), 8.92–8.93 (m, 1 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 16.2 (d, J = 6.8 Hz), 62.2 (d, J = 5.8 Hz), 121.1, 125.9 (d,
J = 1.5 Hz), 128.1 (d, J = 2.2 Hz), 128.5, 129.9 (d, J = 4.9 Hz), 135.0
(d, J = 6.7 Hz), 136.1, 136.4 (d, J = 10.0 Hz), 137.7 (d, J = 177.2 Hz),
4.04–4.15 (m, 4 H), 5.55 (dd, J1 = 1.1, J2 = 47.8 Hz, 1 H), 5.90 (dd,
J1 = 1.0, J2 = 22.3 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 7.3
(d, J = 4.5 Hz), 12.5 (d, J = 15.4 Hz), 16.3 (d, J = 6.3 Hz), 61.9 (d, J =
5.6 Hz), 125.5 (d, J = 10.3 Hz), 140.9 (d, J = 173.3 Hz) ppm. 31P NMR
146.3 (d, J = 5.2 Hz), 149.9 ppm. 31P NMR (202.5 MHz, CDCl3): δ = (202.5 MHz, CDCl3): δ = 19.1 ppm. IR (KBr): ν = 3446, 2985, 1647,
˜
16.3 ppm. IR (KBr): ν = 3481, 2983, 1497, 1473, 1395, 1235, 1053,
1395, 1239, 1209, 1052, 1023, 965 cm–1. GC–MS: m/z (%) = 205 (5)
˜
1020, 961 cm–1. GC–MS: m/z (%) = 291 (4) [M+], 262 (10), 234 (7),
[M + H+], 176 (12), 161 (8), 148 (100), 129 (17), 94 (16), 81 (29), 66
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(53). HRMS (ESI): calcd. for C9H17O3PNa [M + Na]+ 227.0808; found
227.0794.
[12]
[13]
[14]
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I. G. Trostyanskaya, I. P. Beletskaya, Tetrahedron 2014, 70, 2556–2562; d)
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Diethyl [1-(13-Methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-deca-
hydro-6H-cyclopenta[a]phenanthren-3-yl)vinyl]phosphonate
(23): Off-white oil (121.1 mg, 97 % yield). 1H NMR (500 MHz, CDCl3):
δ = 0.91 (s, 3 H), 1.31 (t, J = 7.1 Hz, 6 H), 1.43–1.66 (m, 6 H), 1.95–
2.18 (m, 4 H), 2.28–2.33 (m, 1 H), 2.41–2.45 (m, 1 H), 2.48–2.54 (m,
1 H), 2.92–2.94 (m, 2 H), 4.05–4.18 (m, 4 H), 6.13 (dd, J1 = 1.6, J2 =
45.9 Hz, 1 H), 6.11 (dd, J1 = 1.6, J2 = 22.0 Hz, 1 H), 7.26–7.28 (m, 2
H), 7.32 (d, J = 8.3 Hz, 6 H) ppm. 13C NMR (125 MHz, CDCl3): δ =
13.6, 16.1 (d, J = 6.2 Hz), 21.4, 25.4, 26.3, 29.2, 31.4, 35.6, 37.9, 44.2,
44.7, 50.3, 62.0 (d, J = 5.6 Hz), 124.6 (d, J = 5.5 Hz), 125.2, 127.7 (d,
J = 5.7 Hz), 128.9 (d, J = 170.7 Hz), 130.8 (d, J = 8.0 Hz), 133.9 (d,
J = 11.8 Hz), 136.3, 138.5, 139.8 (d, J = 5.9 Hz) ppm. 31P NMR
[15]
[16]
(202.5 MHz, CDCl3): δ = 17.4 ppm. IR (KBr): ν = 2979, 2930, 2866,
˜
1738, 1455, 1237, 1050, 1023, 963 cm–1. GC–MS: m/z (%) = 416 (29)
[M+], 372 (29), 291 (33), 223 (28), 179 (30), 167 (72), 153 (84), 141
(100), 115 (78), 97 (39), 81 (38). HRMS (ESI): calcd. for C24H33O4PNa
[M + Na]+ 439.2009; found 439.2008.
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Acknowledgments
The National Natural Science Foundation of China (NSFC) (grant
number 21202090), the Zhejiang Provincial Natural Science
Foundation of China (grant number LQ13B010004), the National
Training Programs of Innovation and Entrepreneurship for
Undergraduates (grant number 201411058005), the Xinmiao
Talents Program (grant number 2015R424004), and Ningbo Uni-
versity of Technology (NBUT) are greatly acknowledged for
funding this work. The authors acknowledge Dr. Yinxing Zhang
and Mr. Xie Li for NMR spectra and Dr. Tingting Wang for HRMS
data. Valuable comments from Professor Chaozhong Li (SIOC)
are appreciated.
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Received: November 18, 2015
Published Online: February 16, 2016
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim