Synthesis of α,β-Unsaturated Phosphine Sulfides

Article abstract of DOI:10.1055/s-0039-1690685

α,β-Unsaturated phosphine sulfides may exhibit different reactivity from α,β-unsaturated phosphine oxides toward nucleophilic addition and thus may find new applications in copper(I)-catalyzed asymmetric reactions. Herein, various α,β-unsaturated phosphine sulfides were prepared in moderate to excellent yields from the parent α,β-unsaturated phosphine oxides with Lawesson's reagent. The reaction enjoys a broad substrate scope and tolerates a variety of functional groups.

Full text of DOI:10.1055/s-0039-1690685

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2019, 51, A–I
paper
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en
X.-L. Wang et al.
Paper
Synthesis
Synthesis of ,-Unsaturated Phosphine Sulfides
Xian-Liang Wanga,b
Jin-Xiang Chenb
Xue-Shun Jia*a
O
S
P
R2
Lawesson's reagent
0.05 M, THF, 80 °C
P
R2
R2
R2
R1
R1
R1 = alkyl, aryl
32 examples
up to 99% yield
Liang Yin*b
0
0
0
0-0
0
0
1-9
6
0
4-5
1
9
8
R2 = aryl
a Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai
200444, P. R. of China
xsjia@mail.shu.edu.cn
b CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for
Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry,
University of Chinese Academy of Sciences, Chinese Academy of Sciences,
345 Lingling Road, Shanghai 200032, P. R. of China
liangyin@sioc.ac.cn
Received: 26.07.2019
Accepted after revision: 05.09.2019
Published online: 30.09.2019
the presence of the copper(I) catalyst, which resulted in sig-
nificantly low yield. However, an N-thiophosphinoyl keti-
mine reacted with diethyl phosphite smoothly to afford the
product in 90% yield with 96% ee. Analogously, it is very
reasonable to envision that ,-unsaturated phosphine sul-
fides would find their application in asymmetric reactions
with copper(I) catalysts. Here, we would like to report a
method for the efficient preparation of an array of ,-un-
saturated phosphine sulfides from the parent ,-unsatu-
rated phosphine oxides with Lawesson’s reagent.
DOI: 10.1055/s-0039-1690685; Art ID: ss-2019-f0419-op
Abstract ,-Unsaturated phosphine sulfides may exhibit different re-
activity from ,-unsaturated phosphine oxides toward nucleophilic ad-
dition and thus may find new applications in copper(I)-catalyzed asym-
metric reactions. Herein, various ,-unsaturated phosphine sulfides
were prepared in moderate to excellent yields from the parent ,-un-
saturated phosphine oxides with Lawesson’s reagent. The reaction en-
joys a broad substrate scope and tolerates a variety of functional
groups.
(a) Direct Copper(I)-Catalyzed Asymmetric Vinylogous Michael Addition
Key words phosphine oxides, phosphine sulfides, thionation, Lawesson’s
X
Ph
reagent, thiocarbonyl compounds
X
[Cu], base
THF, rt
Me2N
O
O
Me2N
Ph
‘Soft’ thiocarbonyl compounds may show different reac-
tivities from the parent and ‘hard’ carbonyl compounds in
asymmetric catalysis with soft metal catalysts.1 Thioamides
have been reported as wonderful enolizable substrates in
direct asymmetric aldol, Mannich, and Michael reactions
with copper(I) catalysts.2 However, the parent amides were
hard to enolize under the same reaction conditions and did
not react with aldehydes, imines, and ,-unsaturated com-
pounds to give the target products. Moreover, ,-unsatu-
rated thioamides have served as powerful electrophiles and
enabled various challenging asymmetric reactions in the
presence of copper(I) catalysts.3 For example, the addition
of crotonolactone to an ,-unsaturated amide was found to
be extremely difficult while the reaction with an ,-unsat-
urated thioamide proceeded efficiently to give the adduct
in 84% yield with >20:1 dr and 98% ee (Scheme 1a).3g
O
O
X = O
X = S
10 mol% [Cu], 10 mol% base
no reaction
5 mol% [Cu], 5 mol% base 84%, >20:1 dr, 98% ee
(b) Direct Copper(I)-Catalyzed Asymmetric Hydrophosphonylation
X
X
PPh2
H
[Cu], base
THF, rt
HN
Ph
PPh2
P(OEt)2
O
N
P(OEt)2
O
Ph
X = O
X = S
1 mol% [Cu], 25 mol% base
0.5 mol% [Cu], 25 mol% base
<5%
90%, 96% ee
(c) Synthesis of α,β-Unsaturated Phosphine Sulfides
S
O
S
MeO
P
S
S
P
S
P
R2
P
R2
R2
R2
R1
R1
OMe
potentially suitable
electrophiles
Lawesson's reagent
N-Thiophosphinoyl ketimines also allowed unprece-
dented copper(I)-catalyzed asymmetric nucleophilic addi-
tions.4,5 In 2013, Shibasaki, Kumagai, and co-workers re-
ported a copper(I)-catalyzed asymmetric addition of dialkyl
phosphite to N-thiophosphinoyl ketimines (Scheme 1b).5c It
is noteworthy that an N-phosphinoyl ketimine was inert in
in copper(I)-
catalyzed reactions
Scheme 1 Application of an ,-unsaturated thioamide and N-thio-
phosphinoyl ketimine as efficient electrophiles in copper(I)-catalyzed
asymmetric reactions
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
X.-L. Wang et al.
Paper
Synthesis
2,4-Bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-
2,4-disulfide was named Lawesson’s reagent (LR) due to
Professor Lawesson’s profound contributions for systematic
study on the application of this reagent in organic chemis-
try.6 LR is a mild and convenient thionating agent for ke-
tones, esters, and amides, which allows the preparation of
thioketones, thioesters, and thioamides in good yields.7 Fur-
thermore, LR has been employed in the synthesis of various
heterocyclic compounds containing sulfur atom(s).8 LR
shows advantages over other classical thionating reagents
(such as P4S10), such as commercial availability, easy han-
dling, and relatively high yield in the thionation. The thion-
ation mechanism with LR has been supported both experi-
mentally9 and computationally.10 Recently, new applica-
tions of LR in organic synthesis have emerged.11
The use of LR to transform P=O to P=S has been previ-
ously studied.12 The reaction was generally carried out in
refluxing toluene and good conversion can be accomplished
without affecting some functional groups such as imide,
amide, lactam, and ester. However, substrates bearing an
,-unsaturated moiety remain unexplored. Moreover, ,-
unsaturated phosphine sulfides might give some unexpect-
ed new reactions in which the parent ,-unsaturated
phosphine oxides might not be applied, especially in the
presence of soft copper(I) catalysts.13 Therefore, there is a
need to investigate such a thionation reaction with LR,
which transforms ,-unsaturated phosphine oxides to the
corresponding ,-unsaturated phosphine sulfides (Scheme
1c). Reported approaches toward the synthesis of ,-un-
saturated phosphine sulfides include the addition of sec-
ondary phosphine chalcogenides to alkynes,14 Wittig olefi-
nation,15 and the sulfidation of ,-unsaturated phos-
phines, which were generated by the hydrophosphination
of alkynes.16 Compared to the above-reported examples,
our method with LR represents an easy and straightforward
methodology with a broad substrate scope and good toler-
ance of functional groups.
Table 1 Optimization of the Reaction Conditionsa
O
P
S
P
LR (1.0 equiv)
Ph
Ph
Ph
Ph
0.05 M, THF, 80 °C
Ph
Ph
2a
1a
(2.2 equiv)
Entry
Solvent
Temp (°C)
Yield (%)b
1
2
THF
rt
26
23
–
MeCN
MeOH
DME
toluene
DCM
DMF
DME
DME
DME
THF
rt
3
rt
4
rt
29
19
8
5
rt
6
rt
7
rt
–
8
40
60
80
40
60
80
36
73
82
34
43
96 (89)c
9
10
11
12
13
THF
THF
a Reaction conditions: 1a (0.22 mmol), LR (0.10 mmol).
b Determined by 1H NMR analysis of the crude reaction mixture using
MeNO2 as an internal standard.
c Isolated yield.
cyano) at the para-position generally gave high yields (2b–f)
while the products (2g and 2h) with electron-donating
groups (including methyl and methoxy) were isolated in
moderate yields. Substrates with a halogen atom at the
meta-position were accepted to generate the products (2i
and 2j) in moderate yields. It is interesting to note that the
sterically congested ortho-bromo-substituted substrate
gave the product in quantitative yield (2k). The reaction
conditions were also applicable to heteroaromatic sub-
strates, furnishing the corresponding products (2l–q) in
good to excellent yields.
As for -alkyl-substituted ,-unsaturated phosphine
oxides, both linear and cyclic alkyls were well tolerated to
afford the corresponding products (2r–t) in high yields. Re-
markably, thionation of the substrate with a bulky tert-
butyl group at the -position proceeded nicely, in 83% yield
(2u). Moreover, an ,,,-unsaturated phosphine oxide
was successfully transformed to the corresponding sulfide
in synthetically useful yield (2v). Particularly noteworthy is
product 2w, possessing a TMS substituent at the -position,
which allows further structure elaboration. The alkyls bear-
ing functional groups (including sulfonate, chloride, benzyl
ether, and sulfonamide) were well tolerated without dis-
turbing the target thionation reaction (2x–ab). Lastly, sub-
strates with various aryl groups (including p-tolyl, p-fluoro-
phenyl, 2-naphthyl, and 2-furanyl) on the phosphine center
We commenced with the thionation of 1a in the pres-
ence of LR (Table 1). Considering the unpleasant smell from
LR, 1a was used in 2.2 equivalents to obtain a full conver-
sion of LR. At room temperature, several common solvents
were screened, including THF, MeCN, MeOH, DME, toluene,
DCM, and DMF. The reaction in THF, MeCN, DME, or toluene
generated product 2a in about 20% yield. With DME as the
solvent, the chemical yield increased as the reaction tem-
perature was increased. At 80 °C, 2a was obtained in 82%
yield. The same tendency was observed for the reaction in
THF. Product 2a was isolated in 89% yield at 80 °C (entry
13). Therefore, THF was chosen as the best solvent and the
best reaction temperature was set as 80 °C.
With the optimized reaction conditions in hand, the
substrate scope of ,-unsaturated phosphine oxides was
investigated (Scheme 2). As for -aryl-substituted ,-un-
saturated phosphine oxides, substrates with electron-
withdrawing groups (including halide, trifluoromethyl, and
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

C
X.-L. Wang et al.
Paper
Synthesis
accepted at the -position. Hopefully, these ,-unsaturat-
ed phosphine sulfides will find applications in copper(I)-
catalyzed asymmetric reactions.
O
S
P
R2
LR (1.0 equiv)
P
R2
R2
R2
R1
R1
0.05 M, THF, 80 °C
1
2
(2.2 equiv)
2a, R = H, 89%
2b, R = Ph, 70%
2c, R = F, 92%
Lawesson’s reagent was obtained from Meryer Chemical. The solvents
were purchased as anhydrous solvents from Energy Chemical. ,-
Unsaturated phosphine oxides were prepared according to reported
procedures.17 NMR spectra were acquired on an Agilent 400 or Bruker
S
S
P
2d, R = Br, 66%
2e, R = CF3, 90%
2f, R = CN, 96%
2g, R = CH3, 79%
2h, R = OCH3, 59%
2i, R = Cl, 58%
P
R
Ph
Ph
Ph
2j, R = Br, 63%
Ph
R
1
400 instrument operating at 400, 101, 376, and 162 MHz for H, 13C,
19F, and 31P, respectively. For 1H NMR, chemical shifts are reported in 
ppm referenced to an internal SiMe4 standard. For 13C NMR, chemical
shifts are reported in the scale relative to NMR solvent (CDCl3:  77.0
ppm) as an internal reference. For 19F NMR, chemical shifts are re-
ported in  ppm referenced to an external CFCl3 standard. For 31P
NMR, chemical shifts are reported in  ppm referenced to an external
H3PO4 (85%) standard. Multiplicities are reported using the standard
abbreviations. Mass spectra (ESI) were measured on an Agilent Tech-
nologies 1100 Series LC-MS system. High-resolution mass spectra
(ESI) were measured on a Thermo Scientific LTQ FT Ultra FT-MS in-
strument. IR spectra were recorded on a Thermo Scientific Nicolet iS5
FT-IR spectrometer. Melting points were detected on a Büchi Melting
Point M-565 apparatus.
Br
S
S
S
S
P
N
P
P
P
S
Ph
Ph
Ph
N
Ph
Ph
Ph
Ph
Ph
2k, 98%
2l, 94%
2m, 78%
2n, 91%
S
S
S
P
P
P
O
Ph
Ph
Ph
Ph
Ph
Ph
S
S
2o, 94%
2p, 92%
2q, 99%
S
S
S
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2t, 86%
2r, 91%
2s, 81%
(E)-Diphenyl(styryl)phosphine Sulfide (2a); Typical Procedure for
the Thionation of ,-Unsaturated Phosphine Oxides
S
S
S
P
P
P
Ph
TMS
Ph
,-Unsaturated phosphine oxide 1a (669 mg, 2.2 mmol, 2.2 equiv)
and Lawesson’s reagent (404 mg, 1 mmol, 1.0 equiv) were dissolved in
anhydrous THF (20 mL). The resulting yellow solution was refluxed at
80 °C for 12 h. Then, it was cooled to room temperature. The solvent
was evaporated under reduced pressure. The crude product was puri-
fied by silica gel column chromatography (EtOAc/hexane, 1:4) to pro-
vide pure product 2a.
Ph
Ph
Ph
2u, 83%
2v, 70%
2w, 96%
S
P
S
P
S
P
R
R
TsO
Ph
Ph
Ph
Ph
Ph
Ph
2y, R = Cl, 47%
2z, R = OBn, 61%
2aa, R = NMeTs, 50%
2ab, R = OTs, 60%
2x, 83%
White solid; yield: 570 mg (89%); mp 107–110 °C.
S
P
S
IR (film): 3054, 2924, 1605, 1574, 1479, 1435, 1103, 979, 847, 712
O
S
cm–1
.
R
P
Ph
P
Ph
Ph
1H NMR (400 MHz, CDCl3):  = 7.84–7.78 (m, 4 H), 7.67–7.41 (m, 9 H),
7.38–7.37 (m, 3 H), 6.96 (dd, J = 21.1, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 147.87 (d, J = 6.1 Hz), 134.98 (d, J =
19.4 Hz), 133.36 (d, J = 87.3 Hz), 131.52 (d, J = 2.9 Hz), 131.46 (d, J =
10.7 Hz), 130.09, 128.83, 128.66 (d, J = 12.6 Hz), 127.96 (d, J = 1.1 Hz),
119.65 (d, J = 86.5 Hz).
O
R
2ac, R = Me, 77%
2ad, R = F, 50%
2ae, 76%
2af, 60%
Scheme 2 Substrate scope of ,-unsaturated phosphine oxides. Re-
agents and conditions: 1 (2.2 mmol), LR (1.0 mmol), THF (20 mL); isolat-
ed yields.
31P NMR (162 MHz, CDCl3):  = 37.16.
MS (ESI): m/z [M + H]+ = 321.
HRMS (ESI): m/z [M + H]+ calcd for C20H17PS: 321.0861; found:
321.0862.
were tested. To our joy, these substrates smoothly under-
went the thionation to deliver the products in moderate
yields (2ac–af).
(E)-(2-([1,1′-Biphenyl]-4-yl)vinyl)diphenylphosphine Sulfide (2b)
White solid; yield: 555 mg (70%); mp 145–148 °C.
IR (film): 3053, 3028, 1602, 1485, 1435, 1130, 982, 709 cm–1
In summary, a synthetic pathway for the preparation of
,-unsaturated phosphine sulfides has been developed,
which employs ,-unsaturated phosphine oxides and
Lawesson’s reagent as starting materials. Generally, the ,-
unsaturated phosphine sulfides were isolated in moderate
to excellent yields under mild reaction conditions. The
present reaction enjoys a broad substrate scope. Aryls, het-
eroaryls, simple alkyls, and functionalized alkyls are well
.
1H NMR (400 MHz, CDCl3):  = 7.87–7.79 (m, 4 H), 7.69–7.55 (m, 7 H),
7.55–7.41 (m, 8 H), 7.40–7.32 (m, 1 H), 6.99 (dd, J = 21.1, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 147.38 (d, J = 6.0 Hz), 142.83, 140.10,
133.95 (d, J = 19.5 Hz), 133.42 (d, J = 87.0 Hz), 131.54 (d, J = 3.2 Hz),
131.49 (d, J = 10.6 Hz), 128.88, 128.68 (d, J = 12.6 Hz), 128.48 (d, J = 1.1
Hz), 127.82, 127.47, 127.03, 119.50 (d, J = 86.5 Hz).
31P NMR (162 MHz, CDCl3):  = 37.24.
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

D
X.-L. Wang et al.
Paper
Synthesis
MS (ESI): m/z [M + H]+ = 397.
IR (film): 3053, 2226, 1603, 1480, 1435, 1102, 981, 852, 718 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C26H21PS: 397.1174; found:
397.1172.
1H NMR (400 MHz, CDCl3):  = 7.85–7.75 (m, 4 H), 7.67–7.46 (m, 11
H), 7.12 (dd, J = 20.0, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 145.39 (d, J = 6.4 Hz), 139.11 (d, J =
19.4 Hz), 132.64 (d, J = 87.7 Hz), 132.60, 131.83 (d, J = 2.9 Hz), 131.43
(d, J = 10.7 Hz), 128.82 (d, J = 12.6 Hz), 128.39, 124.36 (d, J = 83.5 Hz),
118.37, 113.12.
31P NMR (162 MHz, CDCl3):  = 36.83.
MS (ESI): m/z [M + H]+ = 346.
(E)-(4-Fluorostyryl)diphenylphosphine Sulfide (2c)
White solid; yield: 622 mg (92%); mp 122–123 °C.
IR (film): 3053, 2924, 1599, 1507, 1438, 1228, 1103, 981, 798, 711
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.84–7.78 (m, 4 H), 7.62–7.40 (m, 9 H),
7.03 (t, J = 8.6 Hz, 2 H), 6.90 (dd, J = 20.8, 16.6 Hz, 1 H).
HRMS (ESI): m/z [M + H]+ calcd for C21H16NPS: 346.0814; found:
13C NMR (101 MHz, CDCl3):  = 163.69 (d, J = 251.0 Hz), 146.58 (d, J =
6.4 Hz), 133.31 (d, J = 87.3 Hz), 131.61 (d, J = 2.9 Hz), 131.43 (d, J =
10.7 Hz), 131.17 (d, J = 3.2 Hz), 129.88 (dd, J = 8.4, 1.1 Hz), 128.72 (d,
J = 12.5 Hz), 119.42 (dd, J = 86.4, 2.4 Hz), 115.94 (d, J = 21.9 Hz).
19F NMR (376 MHz, CDCl3):  = –109.94.
31P NMR (162 MHz, CDCl3):  = 37.13.
MS (ESI): m/z [M + H]+ = 339.
346.0812.
(E)-(4-Methylstyryl)diphenylphosphine Sulfide (2g)
White solid; yield: 528 mg (79%); mp 131–133 °C.
IR (film): 3051, 3022, 1607, 1567, 1478, 1435, 1103, 983, 712 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.85–7.75 (m, 4 H), 7.57 (dd, J = 23.0,
16.6 Hz, 1 H), 7.51–7.38 (m, 8 H), 7.16 (d, J = 7.9 Hz, 2 H), 6.90 (dd, J =
21.3, 16.6 Hz, 1 H), 2.33 (s, 3 H).
13C NMR (101 MHz, CDCl3):  = 147.90 (d, J = 6.1 Hz), 140.48, 133.57
(d, J = 87.1 Hz), 132.30 (d, J = 19.5 Hz), 131.53, 131.46 (d, J = 8.4 Hz),
129.60, 128.68 (d, J = 12.4 Hz), 127.99, 118.27 (d, J = 87.1 Hz), 21.49.
31P NMR (162 MHz, CDCl3):  = 37.30.
MS (ESI): m/z [M + H]+ = 335.
HRMS (ESI): m/z [M + H]+ calcd for C21H19PS: 335.1018; found:
HRMS (ESI): m/z [M + H]+ calcd for C20H16FPS: 339.0767; found:
339.0762.
(E)-(4-Bromostyryl)diphenylphosphine Sulfide (2d)
White solid; yield: 525 mg (66%); mp 146–148 °C.
IR (film): 3080, 3053, 1605, 1586, 1485, 1435, 1103, 981, 849, 713
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.83–7.79 (m, 4 H), 7.58–7.44 (m, 9 H),
7.41–7.39 (m, 2 H), 6.96 (dd, J = 20.6, 16.6 Hz, 1 H).
335.1016.
13C NMR (101 MHz, CDCl3):  = 146.46 (d, J = 6.1 Hz), 133.92 (d, J =
19.5 Hz), 133.16 (d, J = 87.3 Hz), 132.04, 131.61 (d, J = 3.0 Hz), 131.44
(d, J = 10.8 Hz), 129.38, 128.70 (d, J = 12.5 Hz), 124.29, 120.68 (d, J =
85.7 Hz).
31P NMR (162 MHz, CDCl3):  = 37.09.
MS (ESI): m/z [M + H]+ = 399.
(E)-(4-Methoxystyryl)diphenylphosphine Sulfide (2h)
White solid; yield: 413 mg (59%); mp 173–175 °C.
IR (film): 3052, 2930, 2358, 1601, 1571, 1479, 1462, 1435, 1255,
1102, 982, 710 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.84–7.78 (m, 4 H), 7.61–7.40 (m, 9 H),
6.93–6.86 (m, 2 H), 6.78 (dd, J = 21.2, 16.6 Hz, 1 H), 3.83 (s, 3 H).
HRMS (ESI): m/z [M + H]+ calcd for C20H16BrPS: 398.9964; found:
398.9966.
13C NMR (101 MHz, CDCl3):  = 161.17, 147.50 (d, J = 6.4 Hz), 133.74
(d, J = 87.2 Hz), 131.50, 131.39, 129.57, 128.59 (d, J = 12.5 Hz), 127.84
(d, J = 19.6 Hz), 116.53 (d, J = 88.3 Hz), 114.21, 55.38.
31P NMR (162 MHz, CDCl3):  = 37.40.
MS (ESI): m/z [M + H]+ = 351.
(E)-Diphenyl(4-(trifluoromethyl)styryl)phosphine Sulfide (2e)
White solid; yield: 699 mg (90%); mp 149–151 °C.
HRMS (ESI): m/z [M + H]+ calcd for C21H19OPS: 351.0967; found:
351.0965.
IR (film): 3054, 1613, 1574, 1479, 1435, 1323, 1167, 1066, 982, 850,
804, 713 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.86–7.78 (m, 4 H), 7.69–7.57 (m, 5 H),
7.54–7.43 (m, 6 H), 7.11 (dd, J = 20.4, 16.6 Hz, 1 H).
(E)-(3-Chlorostyryl)diphenylphosphine Sulfide (2i)
13C NMR (101 MHz, CDCl3):  = 146.00 (d, J = 6.2 Hz), 138.28 (d, J =
20.2 Hz), 132.90 (d, J = 87.4 Hz), 131.76 (d, J = 2.9 Hz), 131.46 (q, J =
32.6 Hz), 131.45 (d, J = 10.7 Hz), 128.80 (d, J = 12.6 Hz), 128.17, 125.78
(q, J = 3.8 Hz), 123.84 (q, J = 272.3 Hz), 123.05 (d, J = 84.3 Hz).
19F NMR (376 MHz, CDCl3):  = –62.76.
31P NMR (162 MHz, CDCl3):  = 36.92.
MS (ESI): m/z [M + H]+ = 389.
White solid; yield: 411 mg (58%); mp 111–113 °C.
IR (film): 3053, 1607, 1563, 1478, 1307, 1182, 1103, 980, 743 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.84–7.77 (m, 4 H), 7.60–7.43 (m, 8 H),
7.42–7.37 (m, 1 H), 7.35–7.24 (m, 2 H), 6.99 (dd, J = 20.5, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 146.20 (d, J = 6.3 Hz), 136.79 (d, J =
19.6 Hz), 134.85, 133.07 (d, J = 87.5 Hz), 131.64 (d, J = 3.0 Hz), 131.45
(d, J = 10.7 Hz), 130.11, 129.92, 128.72 (d, J = 12.6 Hz), 127.51, 126.36,
121.66 (d, J = 85.1 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C21H16F3PS: 389.0735; found:
389.0731.
31P NMR (162 MHz, CDCl3):  = 36.94.
MS (ESI): m/z [M + H]+ = 355.
(E)-4-(2-(Diphenylphosphorothioyl)vinyl)benzonitrile (2f)
HRMS (ESI): m/z [M + H]+ calcd for C20H16ClPS: 355.0472; found:
355.0470.
White solid; yield: 662 mg (96%); mp 156–157 °C.
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

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Synthesis
(E)-(3-Bromostyryl)diphenylphosphine Sulfide (2j)
White solid; yield: 501 mg (63%); mp 134–136 °C.
13C NMR (101 MHz, CDCl3):  = 150.79, 149.46, 144.17 (d, J = 6.5 Hz),
134.37, 132.82 (d, J = 87.5 Hz), 131.74 (d, J = 3.1 Hz), 131.43 (d, J = 10.7
Hz), 130.67 (d, J = 19.1 Hz), 128.77 (d, J = 12.6 Hz), 123.68, 122.51 (d,
J = 84.7 Hz).
31P NMR (162 MHz, CDCl3):  = 36.96.
MS (ESI): m/z [M + H]+ = 322.
IR (film): 3053, 2924, 1606, 1561, 1476, 1435, 1307, 1103, 980, 823,
713 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.86–7.75 (m, 4 H), 7.69 (s, 1 H), 7.60–
7.41 (m, 9 H), 7.25 (t, J = 7.8 Hz, 1 H), 6.98 (dd, J = 20.5, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 146.09 (d, J = 6.2 Hz), 137.06 (d, J =
19.4 Hz), 133.06 (d, J = 87.4 Hz), 132.83, 131.65 (d, J = 3.0 Hz), 131.45
(d, J = 10.8 Hz), 130.43, 130.39, 128.73 (d, J = 12.6 Hz), 126.83, 122.98,
121.70 (d, J = 85.1 Hz).
31P NMR (162 MHz, CDCl3):  = 36.94.
MS (ESI): m/z [M + H]+ = 399.
HRMS (ESI): m/z [M + H]+ calcd for C20H16BrPS: 398.9966; found:
HRMS (ESI): m/z [M + H]+ calcd for C19H16NPS: 322.0814; found:
322.0810.
(E)-Diphenyl(2-(thiophen-2-yl)vinyl)phosphine Sulfide (2n)
White solid; yield: 593 mg (91%); mp 106–108 °C.
IR (film): 3072, 3019, 1636, 1598, 1479, 1243, 1102, 998, 819, 713
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.84–7.65 (m, 5 H), 7.51–7.39 (m, 6 H),
7.31 (d, J = 5.0 Hz, 1 H), 7.19 (d, J = 3.6 Hz, 1 H), 7.00 (dd, J = 5.1, 3.6 Hz,
1 H), 6.72 (dd, J = 20.3, 16.3 Hz, 1 H).
398.9965.
(E)-(2-Bromostyryl)diphenylphosphine Sulfide (2k)
13C NMR (101 MHz, CDCl3):  = 140.51 (d, J = 22.2 Hz), 140.40 (d, J =
7.4 Hz), 133.41 (d, J = 87.7 Hz), 131.59 (d, J = 3.0 Hz), 131.42 (d, J =
10.8 Hz), 130.37, 128.72 (d, J = 12.6 Hz), 128.26, 128.11, 117.94 (d, J =
87.8 Hz).
31P NMR (162 MHz, CDCl3):  = 36.97.
MS (ESI): m/z [M + H]+ = 327.
White solid; yield: 780 mg (98%); mp 131–133 °C.
IR (film): 3057, 3019, 1600, 1583, 1482, 1462, 1103, 981, 712 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.90–7.74 (m, 5 H), 7.59 (d, J = 7.9 Hz, 1
H), 7.53 (dd, J = 8.0, 1.3 Hz, 1 H), 7.54–7.39 (m, 6 H), 7.31–7.22 (m, 1
H), 7.18–7.12 (m, 1 H), 6.92 (dd, J = 20.7, 16.7 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 145.95 (d, J = 7.2 Hz), 135.00 (d, J =
19.5 Hz), 133.33, 132.71 (d, J = 86.9 Hz), 131.72 (d, J = 3.0 Hz), 131.61
(d, J = 10.7 Hz), 131.05, 128.74 (d, J = 12.6 Hz), 128.03 (d, J = 1.6 Hz),
127.74, 124.95 (d, J = 1.0 Hz), 123.70 (d, J = 84.8 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C18H15PS2: 327.0426; found:
327.0421.
(E)-Diphenyl(2-(thiophen-3-yl)vinyl)phosphine Sulfide (2o)
White solid; yield: 613 mg (94%); mp 117–119 °C.
31P NMR (162 MHz, CDCl3):  = 37.30.
MS (ESI): m/z [M + H]+ = 399.
IR (film): 3072, 3053, 1602, 1573, 1478, 1297, 1102, 978, 832, 743
HRMS (ESI): m/z [M + H]+ calcd for C20H16BrPS: 398.9966; found:
398.9962.
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.80 (m, 4 H), 7.58 (dd, J = 22.6, 16.5
Hz, 1 H), 7.51–7.38 (m, 7 H), 7.29 (m, 2 H), 6.76 (dd, J = 21.3, 16.5 Hz, 1
H).
(E)-Diphenyl(2-(pyridin-2-yl)vinyl)phosphine Sulfide (2l)
White solid; yield: 604 mg (94%); mp 130–133 °C.
13C NMR (101 MHz, CDCl3):  = 141.40 (d, J = 6.4 Hz), 138.22 (d, J =
20.9 Hz), 133.42 (d, J = 87.2 Hz), 131.57 (d, J = 3.0 Hz), 131.46 (d, J =
10.7 Hz), 128.70 (d, J = 12.5 Hz), 127.68, 126.97, 125.31, 118.96 (d, J =
87.0 Hz).
31P NMR (162 MHz, CDCl3):  = 37.29.
MS (ESI): m/z [M + H]+ = 327.
IR (film): 3052, 3003, 1579, 1469, 1435, 1309, 1102, 979, 859, 712
cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.64–8.58 (m, 1 H), 7.88–7.79 (m, 4 H),
7.73–7.64 (m, 3 H), 7.51–7.36 (m, 7 H), 7.23 (dd, J = 7.6, 4.7 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 152.87, 152.67, 149.98, 146.61 (d, J =
6.9 Hz), 137.02, 133.15 (d, J = 87.5 Hz), 131.57 (d, J = 2.9 Hz), 131.42
(d, J = 10.7 Hz), 128.68 (d, J = 12.5 Hz), 124.50 (d, J = 46.7 Hz), 124.40
(d, J = 84.3 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C18H15PS2: 327.0426; found:
327.0421.
31P NMR (162 MHz, CDCl3):  = 36.75.
MS (ESI): m/z [M + H]+ = 322.
HRMS (ESI): m/z [M + H]+ calcd for C19H16NPS: 322.0814; found:
(E)-(2-(Benzo[b]thiophen-3-yl)vinyl)diphenylphosphine Sulfide
(2p)
White solid; yield: 691 mg (92%); mp 163–165 °C.
322.0809.
IR (film): 3063, 3016, 1601, 1479, 1434, 1103, 830, 979, 713 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.97–7.77 (m, 7 H), 7.70 (s, 1 H), 7.52–
7.29 (m, 8 H), 7.06 (dd, J = 21.6, 16.7 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 140.48, 139.68 (d, J = 6.5 Hz), 137.03,
133.43 (d, J = 87.3 Hz), 132.23 (d, J = 20.6 Hz), 131.64 (d, J = 3.0 Hz),
131.51 (d, J = 10.7 Hz), 128.77 (d, J = 12.4 Hz), 127.75 (d, J = 1.8 Hz),
125.07, 124.94, 123.03, 121.99, 120.24 (d, J = 85.9 Hz).
(E)-Diphenyl(2-(pyridin-3-yl)vinyl)phosphine Sulfide (2m)
White solid; yield: 501 mg (78%); mp 135–138 °C.
IR (film): 3051, 2956, 1654, 1607, 1584, 1479, 1435, 1102, 980, 851,
713 cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.76 (s, 1 H), 8.59 (d, J = 4.7 Hz, 1 H),
7.90–7.77 (m, 5 H), 7.68–7.44 (m, 7 H), 7.32 (dd, J = 8.1, 4.8 Hz, 1 H),
7.09 (dd, J = 20.3, 16.7 Hz, 1 H).
31P NMR (162 MHz, CDCl3):  = 37.56.
MS (ESI): m/z [M + H]+ = 377.
HRMS (ESI): m/z [M + H]+ calcd for C22H17PS2: 377.0582; found:
377.0579.
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

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X.-L. Wang et al.
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Synthesis
(E)-(2-(Benzo[b]furan-2-yl)vinyl)diphenylphosphine Sulfide (2q)
White solid; yield: 713 mg (99%); mp 120–122 °C.
13C NMR (101 MHz, CDCl3):  = 157.19 (d, J = 5.4 Hz), 133.93 (d, J =
86.8 Hz), 131.28 (d, J = 10.7 Hz), 131.28 (d, J = 2.9 Hz), 128.52 (d, J =
12.5 Hz), 117.71 (d, J = 88.0 Hz), 16.34 (d, J = 23.2 Hz), 8.67 (d, J = 1.5
Hz).
31P NMR (162 MHz, CDCl3):  = 35.45.
MS (ESI): m/z [M + H]+ = 285.
IR (film): 3054, 2925, 1613, 1573, 1471, 1435, 1325, 1104, 968, 816,
716 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.82 (m, 4 H), 7.62 (dd, J = 24.2, 16.2
Hz, 1 H), 7.55 (d, J = 7.8 Hz, 1 H), 7.50–7.40 (m, 7 H), 7.30 (t, J = 7.7 Hz,
1 H), 7.26–7.12 (m, 2 H), 6.85 (s, 1 H).
HRMS (ESI): m/z [M + H]+ calcd for C17H17PS: 285.0861; found:
13C NMR (101 MHz, CDCl3):  = 155.40, 152.75 (d, J = 21.7 Hz), 134.84
(d, J = 7.7 Hz), 133.33 (d, J = 87.8 Hz), 131.66 (d, J = 3.0 Hz), 131.41 (d,
J = 10.8 Hz), 128.77 (d, J = 12.6 Hz), 128.37 (d, J = 1.4 Hz), 126.40,
123.39, 122.02, 120.46 (d, J = 86.2 Hz), 111.27, 110.48.
285.0858.
(E)-(3,3-Dimethylbut-1-en-1-yl)diphenylphosphine Sulfide (2u)
White solid; yield: 498 mg (83%); mp 118–119 °C.
31P NMR (162 MHz, CDCl3):  = 36.81.
MS (ESI): m/z [M + H]+ = 361.
IR (film): 3050, 3006, 1662, 1609, 1586, 1480, 1435, 1101, 984, 828,
746, 710 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.74 (m, 4 H), 7.52–7.38 (m, 6 H), 6.88
HRMS (ESI): m/z [M + H]+ calcd for C22H17OPS: 361.0810; found:
(dd, J = 23.8, 16.5 Hz, 1 H), 6.25 (dd, J = 23.7, 16.5 Hz, 1 H), 1.12 (s, 9
361.0805.
H).
(E)-(Oct-1-en-1-yl)diphenylphosphine Sulfide (2r)
13C NMR (101 MHz, CDCl3):  = 162.26 (d, J = 2.7 Hz), 133.48 (d, J =
86.2 Hz), 131.06 (d, J = 10.5 Hz), 131.05 (d, J = 2.9 Hz), 128.28 (d, J =
12.3 Hz), 116.62 (d, J = 84.8 Hz), 34.94 (d, J = 15.9 Hz), 28.54 (d, J = 1.4
Hz).
31P NMR (162 MHz, CDCl3):  = 36.35.
MS (ESI): m/z [M + H]+ = 301.
Colorless oil; yield: 597 mg (91%).
IR (film): 3054, 2629, 1617, 1480, 1436, 1103, 1053, 972, 717 cm–1
1H NMR (400 MHz, CDCl3):  = 7.80–7.70 (m, 4 H), 7.51–7.37 (m, 6 H),
6.92–6.79 (m, 1 H), 6.35 (dd, J = 24.2, 16.2 Hz, 1 H), 2.32 (tdd, J = 8.4,
5.9, 1.9 Hz, 2 H), 1.52–1.45 (m, 2 H), 1.37–1.23 (m, 6 H), 0.91–0.83 (m,
3 H).
.
HRMS (ESI): m/z [M + H]+ calcd for C18H21PS: 301.1174; found:
13C NMR (101 MHz, CDCl3):  = 152.96 (d, J = 3.5 Hz), 133.60 (d, J =
86.2 Hz), 131.339 (d, J = 3.0 Hz), 131.338 (d, J = 10.5 Hz), 128.53 (d, J =
12.5 Hz), 121.71 (d, J = 84.7 Hz), 34.14 (d, J = 17.9 Hz), 31.53, 28.84,
27.94 (d, J = 1.4 Hz), 22.55, 14.08.
301.1171.
(E)-(2-(Cyclohex-1-en-1-yl)vinyl)diphenylphosphine Sulfide (2v)
White solid; yield: 454 mg (70%); mp 139–141 °C.
31P NMR (162 MHz, CDCl3):  = 35.69.
MS (ESI): m/z [M + H]+ = 329.
HRMS (ESI): m/z [M + H]+ calcd for C20H25PS: 329.1487; found:
IR (film): 3052, 2928, 1628, 1584, 1480, 1435, 1102, 981, 712 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.77 (m, 4 H), 7.45 (m, 6 H), 7.14 (dd, J
= 22.8, 16.4 Hz, 1 H), 6.22 (dd, J = 22.0, 16.4 Hz, 1 H), 6.11 (m, 1 H),
2.19 (m, 4 H), 1.68 (m, 2 H), 1.60 (m, 2 H).
329.1483.
13C NMR (101 MHz, CDCl3):  = 151.26 (d, J = 5.7 Hz), 138.20 (d, J = 1.4
Hz), 135.12 (d, J = 19.6 Hz), 133.85 (d, J = 86.6 Hz), 131.40 (d, J = 10.7
Hz), 131.29 (d, J = 3.0 Hz), 128.52 (d, J = 12.3 Hz), 115.01 (d, J = 88.4
Hz), 26.29, 24.49, 22.09, 22.05.
31P NMR (162 MHz, CDCl3):  = 37.38.
MS (ESI): m/z [M + H]+ = 325.
(E)-Diphenyl(4-phenylbut-1-en-1-yl)phosphine Sulfide (2s)
Colorless oil; yield: 564 mg (81%).
IR (film): 3054, 2923, 1615, 1480, 1435, 1335, 1102, 971, 780 cm–1
1H NMR (400 MHz, CDCl3):  = 7.62 (m, 4 H), 7.48–7.32 (m, 6 H), 7.29–
7.16 (m, 3 H), 7.13 (d, J = 7.1 Hz, 2 H), 6.89–6.70 (m, 1 H), 6.26 (dd, J =
23.6, 16.3 Hz, 1 H), 2.80 (t, J = 7.4 Hz, 2 H), 2.68–2.57 (m, 2 H).
.
HRMS (ESI): m/z [M + H]+ calcd for C20H21PS: 325.1174; found:
13C NMR (101 MHz, CDCl3):  = 151.23 (d, J = 3.7 Hz), 140.65, 133.32
(d, J = 86.3 Hz), 131.40 (d, J = 10.6 Hz), 131.36 (d, J = 3.4 Hz), 128.56 (d,
J = 7.9 Hz), 128.55, 128.48, 126.14, 123.07 (d, J = 84.2 Hz), 35.69 (d, J =
18.0 Hz), 34.16 (d, J = 1.5 Hz).
325.1171.
(E)-Diphenyl(2-(trimethylsilyl)vinyl)phosphine Sulfide (2w)
White solid; yield: 607 mg (96%); mp 154–156 °C.
31P NMR (162 MHz, CDCl3):  = 35.70.
MS (ESI): m/z [M + H]+ = 349.
HRMS (ESI): m/z [M + H]+ calcd for C22H21PS: 349.1174; found:
IR (film): 3053, 2956, 1478, 1436, 1248, 1053, 988, 837, 717 cm–1
1H NMR (400 MHz, CDCl3):  = 7.76–7.71 (m, 4 H), 7.51–7.42 (m, 6 H),
7.37–7.28 (m, 1 H), 6.93 (dd, J = 31.7, 19.5 Hz, 1 H), 0.16 (s, 9 H).
.
13C NMR (101 MHz, CDCl3):  = 154.29 (d, J = 5.5 Hz), 136.54 (d, J =
69.4 Hz), 132.94 (d, J = 84.1 Hz), 131.48 (d, J = 10.6 Hz), 131.44 (d, J =
2.6 Hz), 128.61 (d, J = 12.3 Hz), –1.66.
31P NMR (162 MHz, CDCl3):  = 37.70.
MS (ESI): m/z [M + H]+ = 317.
349.1170.
(E)-(2-Cyclopropylvinyl)diphenylphosphine Sulfide (2t)
White solid; yield: 489 mg (86%); mp 120–123 °C.
IR (film): 3052, 2925, 1669, 1617, 1573, 1479, 1100, 977, 796, 711
cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C17H21PSSi: 317.0944; found:
317.0942.
1H NMR (400 MHz, CDCl3):  = 7.75 (m, 4 H), 7.49–7.39 (m, 6 H), 6.47–
6.24 (m, 2 H), 1.77–1.69 (m, 1 H), 0.97–0.88 (m, 2 H), 0.71–0.58 (m, 2
H).
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

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X.-L. Wang et al.
Paper
Synthesis
(E)-6-(Diphenylphosphorothioyl)hex-5-en-1-yl 4-Methylbenzene-
sulfonate (2x)
1H NMR (400 MHz, CDCl3):  = 7.76 (m, 4 H), 7.65 (d, J = 8.3 Hz, 2 H),
7.54–7.39 (m, 6 H), 7.31 (d, J = 8.0 Hz, 2 H), 6.91–6.78 (m, 1 H), 6.37
(dd, J = 24.1, 16.2 Hz, 1 H), 2.96 (t, J = 7.1 Hz, 2 H), 2.68 (s, 3 H), 2.42 (s,
3 H), 2.38–2.28 (m, 2 H), 1.52 (m, 4 H), 1.42–1.34 (m, 2 H).
13C NMR (101 MHz, CDCl3):  = 152.40 (d, J = 3.6 Hz), 143.23, 134.38,
133.48 (d, J = 86.3 Hz), 131.36 (d, J = 3.0 Hz), 131.35 (d, J = 10.7 Hz),
129.62, 128.57 (d, J = 12.3 Hz), 127.36, 122.03 (d, J = 84.6 Hz), 49.86,
34.60, 34.00 (d, J = 17.9 Hz), 27.53, 27.31, 26.04, 21.50.
31P NMR (162 MHz, CDCl3):  = 35.71.
MS (ESI): m/z [M + H]+ = 498.
HRMS (ESI): m/z [M + H]+ calcd for C27H32NO2PS2: 498.1685; found:
Colorless oil; yield: 780 mg (83%).
IR (film): 3053, 2925, 1597, 1480, 1436, 1356, 1099, 932, 813, 711
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.81–7.68 (m, 6 H), 7.54–7.39 (m, 6 H),
7.33 (d, J = 8.0 Hz, 2 H), 6.85–6.72 (m, 1 H), 6.35 (dd, J = 23.7, 16.2 Hz,
1 H), 4.02 (t, J = 6.2 Hz, 2 H), 2.43 (s, 3 H), 2.35–2.23 (m, 2 H), 1.71–
1.65 (m, 2 H), 1.60–1.48 (m, 2 H).
13C NMR (101 MHz, CDCl3):  = 151.44 (d, J = 3.7 Hz), 144.84, 133.34
(d, J = 86.5 Hz), 132.87, 131.43 (d, J = 3.0 Hz), 131.32 (d, J = 10.6 Hz),
129.87, 128.59 (d, J = 12.5 Hz), 127.84, 122.60 (d, J = 84.1 Hz), 70.03,
33.21 (d, J = 18.0 Hz), 28.29, 23.93 (d, J = 1.5 Hz), 21.65.
498.1681.
31P NMR (162 MHz, CDCl3):  = 35.62.
MS (ESI): m/z [M + H]+ = 471.
HRMS (ESI): m/z [M + H]+ calcd for C25H27O3PS2: 471.1212; found:
(E)-7-(Diphenylphosphorothioyl)hept-6-en-1-yl 4-Methyl-
benzenesulfonate (2ab)
White solid; yield: 581 mg (60%); mp 38–40 °C.
IR (film): 3053, 2934, 1597, 1435, 1175, 1101, 949, 711 cm–1
.
471.1208.
1H NMR (400 MHz, CDCl3):  = 7.80–7.67 (m, 6 H), 7.45 (m, 6 H), 7.33
(d, J = 8.0 Hz, 2 H), 6.81 (ddt, J = 22.7, 16.2, 6.6 Hz, 1 H), 6.35 (dd, J =
24.0, 16.2 Hz, 1 H), 4.00 (t, J = 6.4 Hz, 2 H), 2.42 (s, 3 H), 2.28 (m, 2 H),
1.67–1.60 (m, 2 H), 1.48–1.40 (m, 2 H), 1.38–1.30 (m, 2 H).
13C NMR (101 MHz, CDCl3):  = 152.11 (d, J = 3.7 Hz), 144.79, 133.86,
132.98 (d, J = 4.3 Hz), 131.41 (d, J = 2.9 Hz), 131.31 (d, J = 10.7 Hz),
129.87, 128.59 (d, J = 12.3 Hz), 127.81, 122.18 (d, J = 84.5 Hz), 70.33,
33.82 (d, J = 18.0 Hz), 28.55, 27.31 (d, J = 1.5 Hz), 24.98, 21.66.
31P NMR (162 MHz, CDCl3):  = 35.62.
MS (ESI): m/z [M + H]+ = 485.
HRMS (ESI): m/z [M + H]+ calcd for C26H29O3PS2: 485.1373; found:
(E)-(5-Chloropent-1-en-1-yl)diphenylphosphine Sulfide (2y)
Colorless oil; yield: 301 mg (47%).
IR (film): 3073, 2989, 1621, 1586, 1479, 1435, 1306, 1102, 975, 818,
710 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.79–7.70 (m, 4 H), 7.53–7.39 (m, 6 H),
6.92–6.79 (m, 1 H), 6.45 (dd, J = 23.6, 16.2 Hz, 1 H), 3.54 (t, J = 6.4 Hz,
2 H), 2.56–2.44 (m, 2 H), 2.06–1.85 (m, 2 H).
13C NMR (101 MHz, CDCl3):  = 150.54 (d, J = 3.9 Hz), 133.35 (d, J =
86.6 Hz), 131.46 (d, J = 3.0 Hz), 131.30 (d, J = 10.6 Hz), 128.62 (d, J =
12.5 Hz), 123.38 (d, J = 83.9 Hz), 44.10, 31.11 (d, J = 18.3 Hz), 30.64 (d,
J = 1.4 Hz).
485.1366.
31P NMR (162 MHz, CDCl3):  = 35.48.
MS (ESI): m/z [M + H]+ = 321.
HRMS (ESI): m/z [M + H]+ calcd for C17H18ClPS: 321.0628; found:
(E)-Styryl(di-p-tolyl)phosphine Sulfide (2ac)
White solid; yield: 536 mg (77%); mp 117–119 °C.
IR (film): 3022, 2919, 1599, 1497, 1102, 979, 709 cm–1
.
321.0624.
1H NMR (400 MHz, CDCl3):  = 7.74–7.63 (m, 4 H), 7.61–7.47 (m, 3 H),
7.41–7.30 (m, 3 H), 7.29–7.21 (m, 4 H), 6.93 (dd, J = 20.9, 16.7 Hz, 1 H),
2.38 (s, 6 H).
(E)-(5-(Benzyloxy)pent-1-en-1-yl)diphenylphosphine Sulfide (2z)
White solid; yield: 478 mg (61%); mp 39–42 °C.
13C NMR (101 MHz, CDCl3):  = 147.24 (d, J = 5.8 Hz), 141.98 (d, J = 2.9
Hz), 135.11 (d, J = 19.3 Hz), 131.49 (d, J = 11.1 Hz), 130.16 (d, J = 89.6
Hz), 129.96, 129.39 (d, J = 13.0 Hz), 128.81, 127.92, 120.27 (d, J = 86.5
Hz), 21.52.
31P NMR (162 MHz, CDCl3):  = 36.64.
MS (ESI): m/z [M + H]+ = 349.
IR (film): 3054, 3005, 1633, 1574, 1479, 1362, 1102, 976, 808, 710
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.79–7.67 (m, 4 H), 7.53–7.37 (m, 6 H),
7.37–7.22 (m, 5 H), 6.94–6.81 (m, 1 H), 6.37 (dd, J = 23.9, 16.2 Hz, 1 H),
4.47 (s, 2 H), 3.49 (t, J = 6.2 Hz, 2 H), 2.45 (m, 2 H), 1.85–1.78 (m, 2 H).
13C NMR (101 MHz, CDCl3):  = 152.05 (d, J = 3.8 Hz), 138.33, 133.49
(d, J = 86.5 Hz), 131.36 (d, J = 2.9 Hz), 131.35 (d, J = 10.7 Hz), 128.55 (d,
J = 12.3 Hz), 128.38, 127.59 (two peaks overlap), 122.28 (d, J = 84.7
Hz), 72.96, 69.24, 30.79 (d, J = 18.2 Hz), 28.18 (d, J = 1.4 Hz).
HRMS (ESI): m/z [M + H]+ calcd for C22H21PS: 349.1174; found:
349.1171.
31P NMR (162 MHz, CDCl3):  = 35.64.
MS (ESI): m/z [M + H]+ = 393.
(E)-Bis(4-fluorophenyl)(styryl)phosphine Sulfide (2ad)
White solid; yield: 356 mg (50%); mp 101–103 °C.
HRMS (ESI): m/z [M + H]+ calcd for C24H25OPS: 393.1436; found:
393.1431.
IR (film): 3060, 2924, 1647, 1575, 1495, 1395, 1175, 979, 828, 711
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.86–7.69 (m, 4 H), 7.63–7.48 (m, 3 H),
7.39 (dd, J = 4.9, 1.9 Hz, 3 H), 7.16 (m, 4 H), 6.91 (dd, J = 21.4, 16.6 Hz,
1 H).
(E)-N-(7-(Diphenylphosphorothioyl)hept-6-en-1-yl)-N,4-di-
methylbenzenesulfonamide (2aa)
13C NMR (101 MHz, CDCl3):  = 164.83 (dd, J = 253.8, 3.3 Hz), 148.26
(d, J = 6.1 Hz), 134.70 (d, J = 19.5 Hz), 133.87 (dd, J = 12.5, 8.8 Hz),
130.35, 129.16 (dd, J = 90.5, 3.4 Hz), 128.91, 128.01, 119.19 (d, J = 88.0
Hz), 116.07 (dd, J = 21.6, 13.9 Hz).
Colorless oil; yield: 497 mg (50%).
IR (film): 3053, 2931, 1614, 1596, 1436, 1338, 1120, 933, 814, 712
cm–1
.
© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

H
X.-L. Wang et al.
Paper
Synthesis
19F NMR (376 MHz, CDCl3):  = –107.21.
31P NMR (162 MHz, CDCl3):  = 35.74.
MS (ESI): m/z [M + H]+ = 357.
References
(1) For the ‘hard and soft acids and bases’ theory, see: (a) Pearson,
R. G. J. Chem. Educ. 1968, 45, 581. (b) Pearson, R. G. J. Chem. Educ.
1968, 45, 643.
HRMS (ESI): m/z [M + H]+ calcd for C20H15F2PS: 357.0673; found:
(2) For some recent examples, see: (a) Iwata, M.; Yazaki, R.; Suzuki,
Y.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2009, 131,
18244. (b) Iwata, M.; Yazaki, R.; Kumagai, N.; Shibasaki, M. Tet-
rahedron: Asymmetry 2010, 21, 1688. (c) Iwata, M.; Yazaki, R.;
Chen, I.; Sureshkumar, D.; Kumagai, N.; Shibasaki, M. J. Am.
Chem. Soc. 2011, 133, 5554. (d) Suzuki, Y.; Yazaki, R.; Kumagai,
N.; Shibasaki, M. Chem. Eur. J. 2011, 17, 11998. (e) Kawato, Y.;
Iwata, M.; Yazaki, R.; Kumagai, N.; Shibasaki, M. Tetrahedron
2011, 67, 6539. (f) Sureshkumar, D.; Kawato, Y.; Iwata, M.;
Kumagai, N.; Shibasaki, M. Org. Lett. 2012, 14, 3018. (g) Suzuki,
Y.; Iwata, M.; Yazaki, R.; Kumagai, N.; Shibasaki, M. J. Org. Chem.
2012, 77, 4496. (h) Gopinath, P.; Watanabe, T.; Shibasaki, M.
J. Org. Chem. 2012, 77, 9260. (i) Kawato, Y.; Chaudhary, S.;
Kumagai, N.; Shibasaki, M. Chem. Eur. J. 2013, 19, 3802.
(j) Alagiri, K.; Lin, S.; Kumagai, N.; Shibasaki, M. Org. Lett. 2014,
16, 5301. (k) Matsuzawa, A.; Opie, C. R.; Kumagai, N.; Shibasaki,
M. Chem. Eur. J. 2014, 20, 68. (l) Bao, Y.; Kumagai, N.; Shibasaki,
M. Chem. Sci. 2015, 6, 6124. (m) Cui, J.; Ohtsuki, A.; Watanabe,
T.; Kumagai, N.; Shibasaki, M. Chem. Eur. J. 2018, 24, 2598.
(n) Ota, Y.; Li, Z.; Kumagai, N.; Shibasaki, M. Synlett 2019, 30,
620.
357.0669.
(E)-Di(naphthalen-2-yl)(styryl)phosphine Sulfide (2ae)
White solid; yield: 639 mg (76%); mp 199–201 °C.
IR (film): 3052, 2923, 1651, 1604, 1590, 1500, 1338, 1081, 979, 859,
741 cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.46 (dd, J = 15.7, 1.5 Hz, 2 H), 7.91–
7.80 (m, 6 H), 7.80–7.66 (m, 3 H), 7.53 (m, 6 H), 7.40–7.31 (m, 3 H),
7.14 (dd, J = 21.3, 16.6 Hz, 1 H).
13C NMR (101 MHz, CDCl3):  = 148.28 (d, J = 6.1 Hz), 135.05 (d, J =
19.5 Hz), 134.53 (d, J = 2.6 Hz), 133.28 (d, J = 10.8 Hz), 132.59 (d, J =
13.9 Hz), 130.43 (d, J = 87.5 Hz), 130.22, 128.97, 128.92, 128.69 (d, J =
12.2 Hz), 128.28, 128.10 (d, J = 1.1 Hz), 127.85, 127.08, 126.50 (d, J =
11.4 Hz), 119.46 (d, J = 86.6 Hz).
31P NMR (162 MHz, CDCl3):  = 37.70.
MS (ESI): m/z [M + H]+ = 421.
HRMS (ESI): m/z [M + H]+ calcd for C28H21PS: 421.1174; found:
421.1170.
(3) For some recent examples, see: (a) Yazaki, R.; Kumagai, N.;
Shibasaki, M. J. Am. Chem. Soc. 2010, 132, 10275. (b) Yanagida,
Y.; Yazaki, R.; Kumagai, N.; Shibasaki, M. Angew. Chem. Int. Ed.
2011, 50, 7910. (c) Yazaki, R.; Kumagai, N.; Shibasaki, M. Org.
Lett. 2011, 13, 952. (d) Yazaki, R.; Kumagai, N.; Shibasaki, M.
Chem. Asian J. 2011, 6, 1778. (e) Ogawa, T.; Kumagai, N.;
Shibasaki, M. Angew. Chem. Int. Ed. 2012, 51, 8551. (f) Ogawa, T.;
Mouri, S.; Yazaki, R.; Kumagai, N.; Shibasaki, M. Org. Lett. 2012,
14, 110. (g) Yin, L.; Takada, H.; Lin, S.; Kumagai, N.; Shibasaki, M.
Angew. Chem. Int. Ed. 2014, 53, 5327. (h) Majumdar, N.; Saito, A.;
Yin, L.; Kumagai, N.; Shibasaki, M. Org. Lett. 2015, 17, 3362.
(4) For the preparation of N-thiophosphinoyl ketimines, see: (a) Xu,
X.; Wang, C.; Zhou, Z.; Zeng, Z.; Ma, X.; Zhao, G.; Tang, C. Lett.
Org. Chem. 2006, 3, 640. (b) Xu, X.; Wang, C.; Zhou, Z.; Zeng, Z.;
Ma, X.; Zhao, G.; Tang, C. Heteroat. Chem. 2008, 19, 238.
(E)-Di(furan-2-yl)(styryl)phosphine Sulfide (2af)
White solid; yield: 360 mg (60%); mp 97–98 °C.
IR (film): 3125, 3024, 1605, 1575, 1494, 1209, 1173, 1053, 978, 850,
740 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.74–7.60 (m, 3 H), 7.59–7.53 (m, 2 H),
7.38 (m, 3 H), 7.15 (m, 2 H), 7.02 (dd, J = 23.1, 16.7 Hz, 1 H), 6.51 (m, 2
H).
13C NMR (101 MHz, CDCl3):  = 148.48 (d, J = 7.3 Hz), 148.46 (d, J = 7.7
Hz), 147.40 (d, J = 125.9 Hz), 134.78 (d, J = 21.4 Hz), 130.34, 128.83,
128.11, 121.89 (d, J = 21.5 Hz), 116.66 (d, J = 96.5 Hz), 111.18 (d, J = 9.2
Hz).
31P NMR (162 MHz, CDCl3):  = 7.52.
MS (ESI): m/z [M + H]+ = 301.
(5) For some recent examples, see: (a) Yin, L.; Takada, H.; Kumagai,
N.; Shibasaki, M. Angew. Chem. Int. Ed. 2013, 52, 7310. (b) Yin,
L.; Otsuka, Y.; Takada, H.; Mouri, S.; Yazaki, R.; Kumagai, N.;
Shibasaki, M. Org. Lett. 2013, 15, 698. (c) Yin, L.; Bao, Y.;
Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc. 2013, 135, 10338.
(d) Lin, S.; Kawato, Y.; Kumagai, N.; Shibasaki, M. Angew. Chem.
Int. Ed. 2015, 54, 5183. (e) Takada, H.; Kumagai, N.; Shibasaki, M.
Org. Lett. 2015, 17, 4762. (f) Lin, S.; Kumagai, N.; Shibasaki, M.
Chem. Eur. J. 2016, 22, 3296. (g) Lin, S.; Kumagai, N.; Shibasaki,
M. Org. Biomol. Chem. 2016, 14, 9725. (h) Lin, S.; Otsuka, Y.; Yin,
L.; Kumagai, N.; Shibasaki, M. Org. Synth. 2017, 94, 313.
(6) (a) Pedersen, B. S.; Scheibye, S.; Nilsson, N. H.; Lawesson, S.-O.
Bull. Soc. Chim. Belg. 1978, 87, 223. (b) Scheibye, S.; Pedersen, B.
S.; Lawesson, S.-O. Bull. Soc. Chim. Belg. 1978, 87, 229.
(c) Pedersen, B. S.; Scheibye, S.; Clausen, K.; Lawesson, S.-O. Bull.
Soc. Chim. Belg. 1978, 87, 293. (d) Fritz, H.; Hug, P.; Lawesson, S.-
O.; Logemann, E.; Pedersen, B. S.; Sauter, H.; Scheibye, S.;
Winkler, T. Bull. Soc. Chim. Belg. 1978, 87, 525.
HRMS (ESI): m/z [M + H]+ calcd for C16H13O2PS: 301.0447; found:
301.0443.
Funding Information
We gratefully acknowledge the financial support from the ‘Thousand
Youth Talents Plan’, the National Natural Science Foundation of China
(No. 21672235 and No. 21871287), the Strategic Priority Research
Program of the Chinese Academy of Sciences (No. XDB20000000), the
CAS Key Laboratory of Synthetic Chemistry of Natural Substances,
and the Shanghai Institute of Organic Chemistry.
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© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I

I
X.-L. Wang et al.
Paper
Synthesis
(7) For reviews, see: (a) Cherkasov, R. A.; Kutyrev, G. A.; Pudovik, A.
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(13) The application of the prepared ,-unsaturated phosphine sul-
fides in copper(I)-catalyzed asymmetric reactions will be
reported in due course.
(10) (a) Legnani, L.; Toma, L.; Caramella, P.; Chiacchio, M. A.; Giofrè,
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19, 1114. (b) Mlostoń, G.; Hamera-Fałdyga, R.; Heimgartner, H.
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E. A.; Kirdyashkina, A. I.; Slepukhin, P. A.; Shiryaev, A. K. Tetra-
hedron Lett. 2018, 59, 1099. (f) Soleimani, E.; Robertson, K. N.;
Pye, C. C.; Clyburne, J. A. C. Dalton Trans. 2018, 47, 6299.
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Malysheva, S. F.; Gusarova, N. K.; Belogorlova, N. A.; Shagun, V.
A.; Albanov, A. I.; Trofimov, B. A. Synthesis 2015, 47, 263.
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González-Soria, M. J.; Martín-García, I.; Radivoy, G.; Alonso, F.
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Shukla, P.; Shanmugam, M.; Shanmugam, M. Organometallics
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(12) For some selected examples, see: (a) Kawashima, T.; Kojima, S.;
Inamoto, N. Chem. Lett. 1989, 849. (b) McKenna, C. E.; Ye, T.-G.;
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© 2019. Thieme. All rights reserved. Synthesis 2019, 51, A–I