Addition of diphenylphosphinodithioic acid and thioacetic acid with vinylidenecyclopropanes: reversed regioselectivities

Article abstract of DOI:10.1016/j.tet.2009.06.090

The reaction of vinylidenecyclopropanes 1 with diphenylphosphinodithioic acid produces the adducts 3 in good to high yields in toluene upon heating at 100 °C within 1 h, whereas adducts 5 are obtained in excellent yields in reversed regioselectivity from

Full text of DOI:10.1016/j.tet.2009.06.090

Tetrahedron 65 (2009) 6815–6821
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Addition of diphenylphosphinodithioic acid and thioacetic acid with
vinylidenecyclopropanes: reversed regioselectivities
*
Wei Li, Min Shi
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 May 2009
Received in revised form 19 June 2009
Accepted 23 June 2009
Available online 26 June 2009
The reaction of vinylidenecyclopropanes 1 with diphenylphosphinodithioic acid produces the adducts 3
in good to high yields in toluene upon heating at 100 ꢀC within 1 h, whereas adducts 5 are obtained in
excellent yields in reversed regioselectivity from the reaction of 1 with thioacetic acid under identical
conditions. The radical reaction processes have been discussed on the basis of deuterium labeling ex-
periment and the control experiments in the presence of radical inhibitors (TEMPO and BHT) or a proton
scavenger (DTBMP).
Keywords:
Ó 2009 Elsevier Ltd. All rights reserved.
Vinylidenecyclopropanes
Radical addition reaction
Diphenylphosphinodithioic acid
Thioacetic acid
Radical inhibitor
Thiophenol
1. Introduction
Vinylidenecyclopropanes (VDCPs) 1 are one of the most re-
markable organic compounds in the area of highly strained small
Thiocarbonyl or thiophosphoryl groups containing compounds
are very useful building blocks in the synthesis of various sulfur-
containing organic compounds1 which play important roles in
biological and chemical processes.2 Thus far, the synthesis of thio-
carbonyl or thiophosphoryl groups containing compounds is very
similar as the preparation of thioethers and their analogues from
the addition of alkenes with thiols achieved by radical initiators3 or
Brønsted acid such as sulfuric and perchloric acids.3a,4 Generally,
the free radical process produces anti-Markovnikov-type adducts,
while the acid-catalyzed/promoted5,6 process leads to Markovni-
kov-type adducts (Scheme 1).
rings, which have an allene moiety connected by a cyclopropane
ring and yet they are thermally stable and reactive substances in
organic synthesis. Much pioneering work has been done for this
kind of particular organic compounds.7,8 However, few reports on
the intermolecular radical reactions of VDCPs to form thiocarbonyl
or thiophosphoryl groups containing compounds or thioethers
have been reported so far. For example, Pasto and co-workers have
reported the radical addition reactions of vinylidenecyclopropane
with 1,1-dichloro-2,2-difluoroethylene or thiophenol to provide the
corresponding addition products in good yields (Scheme 2).9,10 In
the radical addition of vinylidenecyclopropane with thiophenol, the
corresponding 1,2-addition product was obtained in good yield. In
this paper, we wish to disclose that in the reactions of VDCPs 1 with
diphenylphosphinodithioic acid or thioacetic acid upon heating in
toluene, the corresponding thiophosphoryl or thiocarbonyl groups
adducts were obtained in good yields in different regioselectivities.
R2
radical initiator
or H-Rho zeolite
SR3
R1
R2
R1
R3 SH
+
R2
R1
SR3
CH3
acids
R1, R2, R3 = H, aryl
or alkyl groups
2. Results and discussion
Initial examinations were performed by using diphenylvinyli-
denecyclopropane 1a as substrate to react with diphenylphosphino-
dithioic acid 2 in various solvents at different temperatures [from
room temperature (25 ꢀC) to 100 ꢀC] and the results of these ex-
periments are summarized in Table 1. In the presence of radical
initiator such as azobis(isbutyronitrile) (AIBN), we found that the
Scheme 1. Two types of addition of thiols to double bonds.
* Corresponding author. Fax: þ86 21 64166128.
E-mail address: mshi@mail.sioc.ac.cn (M. Shi).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.06.090

6816
W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
CH3
CF2
H3C
CH3
CF2
H3C
C6H5
H
C6H5
H
Cl2C=CF2
C
Cl2C
C6H5
2
Cl2
H3C
H3C
3' 2'
1
.
3
H3C
CH3
H3C
CH3
C6H5
H
C6H5
C6H5SH
SC6H5
SC6H5
H
H
Scheme 2. Radical reactions of VDCP with multi-halo-substituted alkene and thiophenol.
Table 1
Optimization of the reaction conditions of 1a with 2
Ph
S
Ph
Ph
P
Ph
S
Ph
additive (y equiv)
solvent, Ar
+
Ph2P(S)SH
Ph
2, x equiv
1a
3a
Entrya Solvent
Additive
AIBN
x
y
Temp (ꢀC) Time (h) Yield b (%) 3a
1
2
Toluene
Toluene
Toluene
Toluene
Toluene
MeCN
1.1
1.1
1.1
100
100
3
1
4
54
94
3
4
5
6
7
8
9d
TEMPO
BHT
1.0 1.0 100
1.0 1.0 100
dc
4
90
1.0
1.1
1.1
1.1
1.1
25
80
80
70
100
1
1
1
1
Complex
22
53
71
4
DCE
Benzene
DMF
24
a
Reaction conditions: VDCP 1a (0.18 mmol), 2 (x equiv) and additive (y equiv)
were dissolved in toluene (3 mL), then the mixtures were stirred for different time at
various temperatures.
b
Figure 1. The ORTEP drawing of compound 3a.
Isolated yield.
76% of 1a was recovered.
92% of 1a was recovered.
c
d
products (Table 2, entries 1–4). As for the unsymmetrical vinyl-
idenecyclopropanes 1f–k bearing different aryl or alkyl groups at the
C30 position, the corresponding adducts were obtained as mixtures of
E- and Z-isomers in good yields (Table 2, entries 5–10).
corresponding 1,2-addition product 3a was produced in 54% yield
in toluene at 100 ꢀC within 3 h (Table 1, entry 1). Interestingly, in
the absence of any additive, 3a was given in 94% yield under oth-
erwise identical conditions within 1 h (Table 1, entry 2). It was not
surprised that there was nearly none of product 3a obtained in the
presence of radical inhibitor such as 2,2,6,6-tetramethylpiperidine
1-oxyl (TEMPO) along with the recovery of the starting materials 1a
in 76% yield (Table 1, entry 3). However, another radical inhibitor
2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT) has no influence
on the reaction outcome, giving adduct 3a in 90% yield (Table 1,
entry 4). If the reaction was carried out at room temperature
(25 ꢀC), many unidentified products including 3a were produced
within 1 h (Table 1, entry 5). In some other solvents, such as ace-
tonitrile, 1,2-dichloroethane (DCE), benzene and N,N-dime-
thylformamide (DMF), 3a was produced in lower yields than that in
toluene (Table 1, entries 6–9). The structure of 3a has been de-
termined by IR, NMR, MS spectroscopic data and elemental analysis
as well as the X-ray diffraction. The ORTEP drawing is shown in
Figure 1 and its CIF data have been presented in Supplementary
data.11
Table 2
Radical addition reactions of 1 with 2 under the optimal conditions
Ph
S
R
P
R
2
toluene, Ar, 100 °C
1 h
3' 2'
1
Ph
S
+
Ph2P(S)SH
3
Ar
Ar
2, 1.1 equiv
1
3
Entrya
R/Ar
Yieldb (%) 3
1
2
3
4
5
6
7
8
9
10
p-CH3C6H4/p-CH3C6H4, 1b
p-CH3OC6H4/p-CH3OC6H4, 1C
p-ClC6H4/p-ClC6H4, 1d
p-FC6H4/p-FC6H4, 1e
p-CH3OC6H4/C6H4, 1f
p-ClC6H4/C6H4, 1g
3b, 90
3c, 99
3d, 79
3e, 84
3f, 83c
3g, 83d
3h, 82e
3i, 72f
3j, 76g
3k, 78h
p-FC6H4/C6H4, 1h
m,p-di-FC6H4/C6H4, 1i
o-CH3C6H4/C6H4, 1j
CH3/C6H4, 1k
Under these optimized conditions, we next examined the gener-
ality of this transformation using
a
variety of vinyl-
a
Reaction conditions: VDCP 1 (0.18 mmol) and 2 (1.1 equiv) were dissolved in
idenecyclopropanes 1. The results are summarized in Table 2. We
found that the corresponding adducts 3 were obtained in good to
high yields within 1 h whether R1 group of 1 was an aryl or alkyl
group or the electron-donating or -withdrawing groups were in-
troduced on the aromatic rings (Table 2). As for symmetrical diaryl-
vinylidenecyclopropanes 1b–e, the corresponding adducts 3b–e
were obtained in good to excellent yields as the corresponding sole
toluene (3.0 mL), and then the mixtures were stirred for 1 h at 100 ꢀC.
b
Isolated yield.
c
E- or Z-isomeric mixture¼3:2.
d
E- or Z-isomeric mixtures¼1:1.
e
E- or Z-isomeric mixtures¼1:1.
f
E- or Z-isomeric mixtures¼1:1.
g
E- or Z-isomeric mixtures¼2:1.
h
E- or Z-isomeric mixtures¼4:1.

W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
6817
In order to have a clear understanding of the mechanism for this
process, we also examined the reaction of diphenylvinylidenecy-
clopropane 1a with diphenylphosphinodithioic acid 2 under these
optimized reaction conditions in the presence of 1.1 equiv of 2,6-di-
tert-butyl-4-methylpyridine (DTBMP), which has weak nucleophi-
licity and is often used as a scavenger of proton or protic acid.12 We
found that the yield of the product 3a was not affected in this sit-
uation, which can exclude the carbocationic process (run 1, Scheme
3). On the other hand, when the reaction was carried out in the
presence of D2O (10.0 equiv), the corresponding addition product
was formed in 90% yield along with 70% of D content, suggesting
that there is a rapid deuterium–proton exchange between diphe-
nylphosphinodithioic acid and D2O and subsequently a radical re-
action takes place to give the deuterium-containing adduct (run 2,
Scheme 3).
carried out in the presence of DTBMP, the adduct 5a was formed in
65% yield along with the recovery of 10% of 1a (Scheme 4). These
results suggest that the radical process should be the main pathway
in this addition reaction.
On the other hand, we also examined the reaction of diphe-
nylvinylidenecyclopropane 1a with thiophenol 6 (1.1 equiv) in tol-
uene at 100 ꢀC and found that the adduct 8 was given in 95% yield
after 1 h (Scheme 5, Eq. 1). It should be noted that using O,O-diethyl
S-hydrogen phosphorodithioate 7 to replace 2 in the reaction with
1a under identical conditions, the corresponding adduct 9 was
produced in 93% yield as a variety of isomeric mixtures on the basis
of 31P NMR spectrum, presumably attributed to the intramolecular
exchange of sulfur–oxygen atom in product 9 (Scheme 5, Eq. 2).
The reversed regioselectivity could be explained by the steric
effect of the racial intermediates. Generally, the radical intermediate
B is more stable than the vinyl radical intermediate A,13 but the
former is difficult to abstract the hydrogen atom of 2 to give another
sulfur-containing radical species for the next cycle due to the steric
repulsion between the sterically large diphenylphosphinodithioic
acidic radical and the tetramethyl substituted cyclopropane in in-
termediate B. Therefore, the abstraction of a hydrogen atom from 2
by radical intermediate A is sterically favored. However, in the case
of the addition of 1a with 4, the more stable radical intermediate D
can abstract the hydrogen atom from 4 since the thiocarboxylic acid
radical is sterically planar species. Consequently, the additions of 2
to vinylidenecyclopropanes and 4 to vinylidenecyclopropanes have
reversed regioselectivities by undergoing different radical in-
termediates A and D, respectively (Fig. 2).13a
Me
tBu
N
tBu
DTBMP, 1.1 equiv
(1)
(2)
3a
toluene, Ar,
100 °C, 1 h,
95% yield
Ph
Ph
Ph2P(S)SH
+
Ph
S
D
Ph
Ph
P
D2O (10 equiv)
1a
Ph
S
toluene, Ar,
100 °C, 1 h,
90% yield
3a-D
3. Conclusion
70% D
We have disclosed here a previously unknown radical addition
reaction of vinylidenecyclopropanes 1 with diphenylphosphino-
dithioic acid 2 and thioacetic acid 4 in toluene upon heating at 100 ꢀC
within short reaction time to give the corresponding adducts
smoothly. In the case of 1 with diphenylphosphinodithioic acid 2, the
corresponding adducts 3 were obtained in good to high yields.
However, in the case of 1 with thioacetic acid 4 or thiophenol 6, the
corresponding adducts 5 or 8 could be formed in excellent yields in
areversedregioselectivities.Awiderangeofvinylidenecyclopropanes
1 have been examined in these reactions and the plausible radical
reaction processes have been discussed on the basis of deuterium
labeling and the control experiments in the presence of radical in-
hibitors such as TEMPO and BHT or proton scavenger such as DTBMP.
These processes provide novel and efficient synthetic routes for the
preparation of useful thiophosphoryl or thiocarbonyl groups con-
taining compounds under mild conditions which are remarkably
useful compounds serving as building blocks in the synthesis of var-
ious organosulfur containing compounds. Efforts are in progress to
further elucidate the mechanistic details of this reaction and to dis-
close its scope and limitations.
Scheme 3. Control and deuterium labeling experiments in the reaction of 1a with
Ph2P(S)SH.
More interestingly, when using 1.1 equiv of thioacetic acid in-
stead of Ph2P(S)SH to react with diphenylvinylidenecyclopropane
1a under identical conditions, we found that the adduct 5a was
produced in 94% yield (Table 3, entry 1). In order to confirm this
unexpected regioselectivity, a variety of vinylidenecyclopropanes 1
were examined in this reaction and the results are shown in Table 3.
As for symmetrical vinylidenecyclopropanes having either elec-
tron-donating or -withdrawing groups on the benzene rings, the
corresponding adducts 5 were obtained in excellent yields within
0.5 h (Table 2, entries 2–5).
Table 3
Addition reactions of 1 with thiocarboxylic acid
S
Ar
Ar
Ar
Ar
O
O
2
3
2'
1
3 '
toluene, Ar, 100 °C
0.5 h
+
SH
1
4, 1.1 equiv
5
4. Experimental section
4.1. General methods
Entrya
Ar
Yieldb (%) 5
1
2
3
4
5
C6H5, 1a
5a, 94
5b, 99
5c, 96
5d, 96
5e, 99
p-CH3C6H4, 1b
p-CH3OC6H4, 1c
p-ClC6H4, 1d
p-FC6H4, 1e
1H, 13C, 19F and 31P NMR spectra were recorded at 300 or 400, 75
or 100, 282, and 121.45 MHz respectively. Mass spectra were
recorded by EI and MALDI methods, and HRMS was measured on
Kratos Analytical Concept mass spectrometer (EI), Bruker FT mass
spectrometer (ESI), and IonSpec 4.7 Tesla FTMS (MALDI). Organic
solvents used were dried by standard methods when necessary.
Commercially available reagents were used without further puri-
fication. All reactions were monitored by TLC with Yinlong GF254
silica gel coated plates. Flash column chromatography was carried
out using 300–400 mesh silica gel at increased pressure.
a
Reaction conditions: VDCP 1 (0.18 mmol) and 4 (1.1 equiv) were dissolved in
toluene (3.0 mL), and then the mixtures were stirred for 0.5 h at 100 ꢀC.
b
Isolated yield.
When radical inhibitors, such as TEMPO and BHT, were added in
this reaction system, it was found that the yields of addition
product 5a dropped to 21% and 19%, along with the recovery of 68%
and 64% of the substrate 1a, respectively. When the reaction was

6818
W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
S
Ph
Ph
O
Ph
Ph
O
additive (1.1 equiv)
+
SH
4, 1.1 equiv
toluene, Ar, 100 °C, 0.5 h
5a
1a
BHT: 21% yield with 68% of 1a recovered;
TEMPO: 19% yield with 64% of 1a recovered;
DTBMP: 65% yield with 10% of 1a recovered.
Scheme 4. Reactions of 1a with thiocarboxylic acid in the presence of additives.
4.2. General procedure for the cycloaddition of
vinylidenecyclopropanes 1 with diphenylphosphinodithioic
acid 2 or thioacetic acid 4
Ph
S
Ph
P
H
.
S
S
S
Ph
Ph
S
S
Ph
Ph
P
S
S
P
Ph
Ph
H
Under argon atmosphere, vinylidenecyclopropanes (VDCPs) 1
(0.18 mmol) and diphenylphosphinodithioic acid 2 or thioacetic
acid 4 (0.20 mmol, 1.1 equiv) were dissolved in toluene (3.0 mL),
and then the resulting mixtures were stirred for 0.5 to 1.0 h at
100 ꢀC. The solvent was removed in vacuo and the residue was
purified by flash column chromatography on silica gel column with
petroleum ether–EtOAc (40:1) as an eluent.
Ph
Ph
Ph
Ph
P
vs
.
A
B
4.2.1. 1-(2,2-Diphenylvinyl)-2,2,3,3-tetramethylcyclopropyl
diphenylphosphinodithioate 2a
C
O
O
C
S
O
C
A white solid, Mp: 202–204 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
H
O
C
S
H
d
0.38 (s, 3H, CH3), 1.07 (s, 3H, CH3), 1.23 (s, 3H, CH3), 1.48 (s, 3H,
Ph
Ph
Ph
Ph
S
.
vs
CH3), 6.19 (s, 1H, CH), 6.86 (d, J¼6.3 Hz, 2H, Ar), 7.07–7.15 (m, 6H,
.
S
Ar), 7.23–7.41 (m, 8H, Ar), 7.73 (dd, J¼7.5, 13.5 Hz, 2H, Ar), 7.91 (dd,
J¼6.9, 13.8 Hz, 2H, Ar). 13C NMR (CDCl3, 75 MHz, TMS)
d 19.3, 19.6
(d, JC–P¼13.6 Hz), 21.3, 27.9, 30.5 (d, JC–P¼6.4 Hz), 41.4 (d, JC–P
¼
C
D
3.8 Hz), 126.8, 127.1, 127.3, 127.4, 127.7 (d, JC–P¼13.5 Hz), 128.2, 128.3
(d, JC–P¼17.3 Hz), 129.7 (d, JC–P¼2.1 Hz), 130.4, 130.7 (d, JC–P¼7.7 Hz),
130.9, 131.3, 131.9 (d, JC–P¼11.3 Hz), 134.1 (d, JC–P¼84.4 Hz), 136.3 (d,
JC–P¼85.5 Hz), 140.6, 143.3, 143.4. 31P NMR (CDCl3, 121.45 MHz, 85%
Figure 2. The two types of radical species of the addition reaction.
H3PO4)
d
59.5. IR (CH2Cl2)
n
3055, 2919, 2866,1714,1634,1436,1375,
2.30 (s, 3H, CH3), 2.36 (s, 3H, CH3), 6.10 (s, 1H, CH), 6.74 (d, J¼8.4 Hz,
2H, Ar), 6.91 (d, J¼8.4 Hz, 2H, Ar), 7.06–7.08 (m, 5H, Ar), 7.24–7.37
(m, 5H, Ar), 7.72 (dd, J¼7.2, 13.5 Hz, 2H, Ar), 7.89 (dd, J¼6.9, 14.4 Hz,
1096, 1027, 768, 718, 697, 651 cmꢁ1. MS (%) m/e 524 (Mþ, 5), 307
(100), 291 (19), 275 (25), 259 (29), 233 (49), 223 (83), 121 (27), 91
(25). Anal. Calcd for C33H33S2: C, 75.54%; H, 6.34%. Found: C, 75.56%;
H, 6.20%.
2H, Ar). 13C NMR (CDCl3, 75 MHz, TMS)
d
19.3, 19.7 (d, JC–P¼11.5 Hz),
21.0, 21.3, 27.9, 30.5 (d, JC–P¼6.5 Hz), 41.6 (d, JC–P¼3.5 Hz), 127.7 (d,
JC–P¼13.4 Hz), 128.0, 128.2, 128.4, 128.5 (d, JC–P¼2.0 Hz), 130.3, 130.7
4.2.2. 1-(2,2-Di-p-tolylvinyl)-2,2,3,3-tetramethylcyclopropyl
diphenylphosphinodithioate 2b
(d, JC–P¼10.7 Hz), 131.3, 131.9 (d, JC–P¼11.3 Hz), 134.2 (d, JC–P¼
84.1 Hz), 136.3, 136.4 (d, JC–P¼85.8 Hz), 136.7, 136.9, 137.7, 140.8,
143.2. 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
55.3. IR (CH2Cl2)
3054, 2999, 2918, 2866, 1510, 1436, 1374, 1096, 823, 718, 689, 655,
A white solid, Mp: 184–186 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
d
n
d
0.41 (s, 3H, CH3),1.08 (s, 3H, CH3),1.22 (s, 3H, CH3),1.47 (s, 3H, CH3),
PhSH
Ph
SPh
6
, 1.1 equiv
(1)
(2)
95% yield
Ph
Ph
Ph
8
.
1a
OEt
SEt
S
O
Ph
Ph
Ph
93% yield
S
P
P
OEt
OEt
S
+
S
Ph
EtO
SH
P
OEt
, 1.1 equiv
7
OEt
SEt
S
O
Ph
Ph
Ph
P
P
SEt
SEt
+
O
+
O
Ph
9
Scheme 5. Reactions of 1a with two other sulfur-containing compounds.

W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
6819
525 cmꢁ1. MS (%) m/e 552 (Mþ, 0.3), 383 (0.3), 335 (100), 302 (2.0),
287 (2.4), 261 (1.4), 251 (1.9), 216 (0.9), 210 (1.6). HRMS (EI) for
C35H37S2P: 552.2074. Found: 552.2076.
7.05–7.15 (m, 6H, Ar), 7.34–7.38 (m, 5H, Ar), 7.72 (dd, J¼7.5, 13.5 Hz,
2H, Ar), 7.91 (dd, J¼7.2, 14.4 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz,
TMS)
d
19.2, 19.6 (d, JC–P¼14.4 Hz), 21.3, 22.6, 27.9, 30.4 (d, JC–P¼
7.2 Hz), 31.6, 41.6 (d, JC–P¼4.1 Hz), 55.2, 112.7, 126.8, 127.4, 127.7 (d,
4.2.3. 1-(2,2-Bis(4-methoxyphenyl)vinyl)-2,2,3,3-
JC–P¼13.3 Hz), 128.3, 128.4, 128.7 (d, JC–P¼1.9 Hz), 130.7 (d, JC–P¼
tetramethylcyclopropyl diphenylphosphinodithioate 2c
11.1 Hz), 131.0, 131.3, 131.6, 131.9 (d, JC–P¼11.1 Hz), 133.0, 134.1 (d, JC–
A white solid, Mp: 138–140 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
¼84.0 Hz), 136.3 (d, JC–P¼85.6 Hz), 143.1, 143.6, 158.6. 31P NMR
P
d
0.41 (s, 3H, CH3), 1.08 (s, 3H, CH3), 1.22 (s, 3H, CH3), 1.48 (s, 3H,
(CDCl3, 121.45 MHz, 85% H3PO4) d 55.2. IR (CH2Cl2) n 3056, 2999,
CH3), 3.77 (s, 3H, OCH3), 3.80 (s, 3H, OCH3), 6.02 (s, 1H, CH), 6.64 (d,
J¼6.9 Hz, 2H, Ar), 6.76–6.83 (m, 4H, Ar), 7.06–7.10 (m, 3H, Ar), 7.34–
7.37 (m, 5H, Ar), 7.73 (dd, J¼6.6, 13.8 Hz, 2H, Ar), 7.92 (dd, J¼6.6,
2917, 2867, 2835, 1606, 1510, 1437, 1374, 1295, 1248, 1178, 1096,
1034, 908, 839, 718, 690, 655, 641, 606, 526 cmꢁ1. MS (%) m/e 554
(Mþ, 2), 337 (100), 304 (36), 289 (52), 263 (41), 253 (57), 217 (31),
165 (17), 139 (20). HRMS (EI) for C34H35S2OP: 554.1867. Found:
554.1864.
14.4 Hz, 2H, Ar). 13C NMR (CDCl3, 75 MHz, TMS)
d
19.2, 19.6 (d, JC–P
¼
12.8 Hz), 21.3, 27.8, 30.3 (d, JC–P¼6.2 Hz), 41.7 (d, JC–P¼3.1 Hz), 55.1,
55.2, 112.6, 112.7, 127.3, 127.5 (d, JC–P¼13.1 Hz), 128.3 (d, JC–P
¼
12.8 Hz), 129.3, 130.6, 130.7, 131.3, 131.6, 131.9 (d, JC–P¼10.7 Hz),
133.2, 134.1 (d, JC–P¼83.7 Hz), 136.26, 136.30 (d, JC–P¼84.8 Hz),
4.2.7. (Z or E)-5-(4-Methoxyphenyl)-2-methyl-5-phenyl-3-
(propan-2-ylidene)pent-4-en-2-yl diphenylphosphinodithioate 2f0
A white solid, Mp: 105–107 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
142.4, 158.6, 158.7. 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
d 59.9.
IR (CH2Cl2)
n
3055, 2998, 2916, 2835, 1606, 1510, 1437, 1289, 1246,
d 0.36 (s, 3H, CH3), 1.06 (s, 3H, CH3), 1.22 (s, 3H, CH3), 1.48 (s, 3H,
1174, 1096, 1035, 834, 717, 690, 655, 526 cmꢁ1. MS (%) m/e 367
(MþꢁPh2PS, 58), 334 (84), 319 (100), 293 (21), 278 (28), 250 (27),
217 (49), 121 (48), 43 (45). HRMS (EI) for C35H37S2O2P: 584.1973.
Found: 584.1984.
CH3), 3.79 (s, 3H, OCH3), 6.12 (s, 1H, CH), 6.66 (d, J¼9.2 Hz, 2H, Ar),
6.80 (d, J¼9.2 Hz, 2H, Ar), 7.07–7.11 (m, 3H, Ar), 7.25–7.27 (m, 3H,
Ar), 7.38–7.43 (m, 5H, Ar), 7.73 (dd, J¼7.5, 13.5 Hz, 2H, Ar), 7.92 (dd,
J¼7.2, 13.8 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 19.3, 19.7
(d, JC–P¼20.9 Hz), 21.3, 27.8, 30.4 (d, JC–P¼7.2 Hz), 41.6 (d, JC–P
¼
4.2.4. 1-(2,2-Bis(4-chlorophenyl)vinyl)-2,2,3,3-
3.3 Hz), 55.2, 112.8, 127.0, 127.3, 127.8 (d, JC–P¼13.5 Hz), 128.3, 128.4,
129.3, 130.4, 130.7 (d, JC–P¼12.0 Hz), 131.3, 131.9 (d, JC–P¼10.3 Hz),
134.2 (d, JC–P¼84.8 Hz), 136.0, 136.3 (d, JC–P¼84.7 Hz), 140.8, 142.8,
tetramethylcyclopropyl diphenylphosphinodithioate 2d
A white solid, Mp: 191–193 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
d
0.45 (s, 3H, CH3), 1.09 (s, 3H, CH3), 1.22 (s, 3H, CH3), 1.48 (s, 3H,
158.8. 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
d 59.9. IR (CH2Cl2) n
CH3), 6.21 (s, 1H, CH), 6.76 (d, J¼8.7 Hz, 2H, Ar), 7.07–7.10 (m, 5H,
Ar), 7.22–7.30 (m, 4H, Ar), 7.36–7.38 (m, 3H, Ar), 7.71 (dd, J¼6.9,
13.2 Hz, 2H, Ar), 7.88 (dd, J¼6.9, 13.5 Hz, 2H, Ar). 13C NMR (CDCl3,
3056, 2999, 2918, 2867, 2835, 1714, 1605, 1509, 1437, 1246, 1096,
1035, 826, 718, 690, 647, 615 cmꢁ1. MS (%) m/e 554 (Mþ, 2), 337
(100), 304 (14), 289 (19), 263 (35), 253 (51), 217 (24), 165 (9), 121
(12). HRMS (EI) for C34H35S2OP: 554.1867. Found: 554.1863.
75 MHz, TMS)
d
19.3, 19.7 (d, JC–P¼19.7 Hz), 21.2, 28.0, 30.6 (d, JC–P
¼
5.7 Hz), 41.0 (d, JC–P¼3.2 Hz), 127.70, 127.74, 127.9, 128.4 (d, JC–P
¼
13.2 Hz), 129.3, 130.7 (d, JC–P¼10.4 Hz), 130.9, 131.0, 131.1, 131.6,
4.2.8. 1-(2-(4-Chlorophenyl)-2-phenylvinyl)-2,2,3,3-
tetramethylcyclopropyl diphenylphosphinodithioate 2g
The ratio of E/Z¼1:1. A light yellow solid, Mp: 98–100 ꢀC; 1H
131.9 (d, JC–P¼10.9 Hz), 133.0 (d, JC–P¼20.6 Hz), 134.1 (d, JC–P
¼
84.7 Hz), 136.1 (d, JC–P¼85.4 Hz), 138.5, 141.0, 141.4. 31P NMR (CDCl3,
121.45 MHz, 85% H3PO4)
d
60.0. IR (CH2Cl2)
n
3055, 2998, 2918,
NMR (CDCl3, 300 MHz, TMS) d 0.36 (s, 1.6H, CH3), 0.45 (s, 1.4H, CH3),
2859, 1716, 1491, 1436, 1375, 1217, 1093, 1014, 833, 719, 689, 653,
518 cmꢁ1. MS (%) m/e 592 (Mþ, 7), 518 (6), 375 (100), 327 (31), 291
(80), 217 (60), 155 (33), 139 (66), 125 (27). HRMS (EI) for
C33H31S2PCl2: 592.0982. Found: 592.0980.
1.06–1.09 (m, 3H, CH3),1.21–1.25 (m, 3H, CH3),1.48 (s, 3H, CH3), 6.18
(s, 0.5H, CH), 6.21 (s, 0.5H, CH), 6.77–6.85 (m, 2H, Ar), 7.06–7.17 (m,
4H, Ar), 7.23–7.40 (m, 9H, Ar), 7.68–7.75 (m, 2H, Ar), 7.84–7.95 (m,
2H, Ar). 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
d
55.15, 55.21. IR
(CH2Cl2)
n 3056, 2998, 2945, 2918, 2867, 1980, 1592, 1487, 1437,
4.2.5. 1-(2,2-Bis(4-fluorophenyl)vinyl)-2,2,3,3-
1375, 1306, 1185, 1095, 1014, 908, 822, 733, 719, 690, 654, 525 cmꢁ1
.
tetramethylcyclopropyl diphenylphosphinodithioate 2e
MS (%) m/e 558 (Mþ, 4), 356 (8), 341 (100), 308 (45), 293 (60), 257
(87), 217 (57), 165 (34), 139 (39). HRMS (EI) for C33H32S2PCl:
558.1372. Found: 558.1366.
A white solid, Mp: 165–167 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
d
0.40 (s, 3H, CH3),1.08 (s, 3H, CH3),1.22 (s, 3H, CH3),1.49 (s, 3H, CH3),
6.14 (s, 1H, CH), 6.80 (d, J¼6.6 Hz, 4H, Ar), 6.94–7.00 (m, 2H, Ar), 7.12
(br s, 3H, Ar), 7.33–7.38 (m, 5H, Ar), 7.71 (dd, J¼7.2, 13.8 Hz, 2H, Ar),
7.91 (dd, J¼7.2, 13.8 Hz, 2H, Ar). 13C NMR (CDCl3, 75 MHz, TMS)
4.2.9. 1-(2-(4-Fluorophenyl)-2-phenylvinyl)-2,2,3,3-
tetramethylcyclopropyl diphenylphosphinodithioate 2h
d
19.2, 19.7 (d, JC–P¼17.3 Hz), 21.2, 27.9, 30.4 (d, JC–P¼6.0 Hz), 41.2 (d,
The ratio of E/Z¼1:1. A light yellow solid, Mp: 88–90 ꢀC; 1H NMR
JC–P¼3.5 Hz), 114.3 (d, JC–F¼21.2 Hz), 114.4 (d, JC–F¼21.4 Hz), 127.7 (d,
JC–P¼13.2 Hz), 128.4 (d, JC–P¼13.5 Hz), 129.6 (d, JC–F¼8.3 Hz), 129.8,
130.7 (d, JC–P¼11.0 Hz),131.0,131.5,131.8,131.9 (d, JC–P¼7.2 Hz),134.1
(d, JC–P¼84.5 Hz),136.1 (d, JC–P¼85.6 Hz),136.3 (d, JC–F¼3.1 Hz),139.2
(CDCl3, 400 MHz, TMS) d 0.35 (s,1.5H, CH3), 0.43 (s,1.5H, CH3), 1.06–
1.08 (m, 3H, CH3), 1.22–1.26 (m, 3H, CH3), 1.49 (s, 3H, CH3), 6.14 (s,
0.5H, CH), 6.19 (s, 0.5H, CH), 6.79–6.85 (m, 3H, Ar), 6.94–6.98 (m,
1H, Ar), 7.09–7.16 (m, 4H, Ar), 7.26–7.28 (m, 2H, Ar), 7.34–7.41 (m,
5H, Ar), 7.70–7.75 (m, 2H, Ar), 7.86–7.96 (m, 2H, Ar). 31P NMR
(d, JC–F¼2.9 Hz), 141.2, 161.9 (d, JC–F¼246.3 Hz), 162.1 (d, JC–F
¼
244.2 Hz). 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
(CDCl3, 282 MHz, CFCl3)
d
55.1. 19F NMR
3055, 2999,
(CDCl3, 121.45 MHz, 85% H3PO4)
282 MHz, CFCl3)
2867, 1715, 1600, 1507, 1437, 1375, 1224, 1158, 1096, 845, 718, 690,
656, 525 cmꢁ1. MS (%) m/e 542 (Mþ, 5), 468 (2), 325 (100), 309 (18),
277 (29), 251 (49), 241 (81), 217 (26), 139 (32). HRMS (EI) for
C33H32S2PF: 542.1667. Found: 542.1674.
d
55.31, 55.34. 19F NMR (CDCl3,
3055, 2999, 2918,
d
ꢁ119.7, ꢁ121.2. IR (CH2Cl2)
n
d
ꢁ121.6, ꢁ120.1. IR (CH2Cl2)
n
2919, 2868, 1600, 1508, 1437, 1375, 1229, 1157, 1096, 1015, 910, 840,
718, 690, 656, 525 cmꢁ1. MS (%) m/e 560 (Mþ, 3), 486 (3), 343 (100),
269 (49), 259 (100), 217 (39), 183 (25), 139 (86), 109 (30). HRMS (EI)
for C33H31S2PF2: 560.1573. Found: 560.1571.
4.2.6. (E or Z)-1-(2-(4-Methoxyphenyl)-2-phenylvinyl)-2,2,3,3-
tetramethylcyclopropyl diphenylphosphinodithioate 2f
4.2.10. 1-(2-(3,4-Difluorophenyl)-2-phenylvinyl)-2,2,3,3-
tetramethylcyclopropyl diphenylphosphinodithioate 2i
The ratio of E/Z¼1:1. A light yellow solid, Mp: 109–111 ꢀC; 1H
A white solid, Mp: 111–1113 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
d
0.41 (s, 3H, CH3), 1.09 (s, 3H, CH3), 1.23 (s, 3H, CH3), 1.49 (s, 3H,
NMR (CDCl3, 300 MHz, TMS) d 0.33 (s, 1.5H, CH3), 0.53 (s, 1.5H, CH3),
CH3), 3.82 (s, 3H, OCH3), 6.08 (s, 1H, CH), 6.81–6.85 (m, 4H, Ar),
1.06–1.14 (m, 3H, CH3), 1.21–1.25 (m, 3H, CH3), 1.49 (s, 3H, CH3), 6.16

6820
W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
(s, 0.5H, CH), 6.23 (s, 0.5H, CH), 6.48–6.55 (m, 0.5H, Ar), 6.64–6.69
(m, 0.5H, Ar), 6.84–6.87 (m, 1H, Ar), 7.01–7.06 (m, 1H, Ar), 7.11–7.30
(m, 5H, Ar), 7.36–7.41 (m, 6H, Ar), 7.68–7.75 (m, 2H, Ar), 7.82–7.99
137.6,139.2,140.3, 154.5, 193.8. IR (CH2Cl2) n 3022, 2976, 2919, 2867,
1696, 1509, 1450, 1376, 1350, 1113, 945, 819, 620 cmꢁ1. MS (%) m/e
378 (Mþ, 2), 335 (100), 261 (12), 219 (10),189 (7), 165 (5), 105 (8), 97
(25), 57 (11). HRMS (EI) for C25H30SO: 378.2017. Found: 378.2023.
(m, 2H, Ar). 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
d
55.0, 55.4.
19F NMR (CDCl3, 282 MHz, CFCl3)
d
ꢁ146.1, ꢁ144.73, ꢁ144.68,
ꢁ144.4. IR (CH2Cl2)
n
3056, 2998, 2918, 2868, 1805, 1714, 1513, 1436,
4.2.16. S-2,2-Bis(4-methoxyphenyl)-1-(2,2,3,3-
1278, 1096, 777, 747, 718, 690, 652, 615 cmꢁ1. MS (%) m/e 560 (Mþ,
5), 343 (52), 295 (18), 259 (31), 217 (32), 139 (23), 86 (63), 84 (100),
49 (100). HRMS (EI) for C33H3S2PF2: 560.1573. Found: 560.1577.
tetramethylcyclopropyl)vinyl ethanethioate 5c
A white solid, Mp: 78–80 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
d
0.63 (s, 6H, 2CH3), 0.95 (s, 6H, 2CH3), 1.77 (s, 1H, CH), 2.12 (s, 3H,
CH3), 3.80 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 6.78 (d, J¼8.8 Hz, 2H,
4.2.11. 2,2,3,3-Tetramethyl-1-(2-phenyl-2-o-tolylvinyl)cyclopropyl
diphenylphosphinodithioate 2j
Ar), 6.79 (d, J¼8.8 Hz, 2H, Ar), 6.99 (d, J¼8.8 Hz, 2H, Ar), 7.24 (d,
J¼8.8 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d 18.3, 23.0, 25.1,
The ratio of E/Z¼2:1. A white solid, Mp: 83–85 ꢀC; 1H NMR
30.1, 40.0, 55.1, 55.2, 112.6, 112.9, 125.2, 131.0, 132.1, 134.8, 135.8,
(CDCl3, 300 MHz, TMS)
d
0.33 (s, 3H, CH3), 0.70 (s, 1.5H, CH3), 0.94–
153.8, 158.8, 159.3, 193.9. IR (CH2Cl2) n 3033, 2947, 2868, 2836,1693,
0.98 (m, 3H, CH3), 1.23–1.25 (m, 6H, 2CH3), 1.48 (s, 3H, CH3), 1.56 (s,
3H, CH3), 1.78 (s, 1.5H, CH3), 6.09 (s, 0.5H, CH), 6.33 (s, 1H, CH), 6.50
(d, J¼7.8 Hz, 0.5H, Ar), 6.78 (d, J¼6.9 Hz, 2H, Ar), 6.94–7.09 (m, 8H,
Ar), 7.19–7.38 (m, 12H, Ar), 7.64–8.00 (m, 7H, Ar). 31P NMR (CDCl3,
1605, 1509, 1463, 1376, 1299, 1247, 1173, 1111, 1035, 945, 833, 817,
618, 561 cmꢁ1. MS (%) m/e 367 (MþꢁCH3CO, 100), 337 (7), 283 (10),
251 (10), 212 (8), 117 (12), 105 (12), 97 (15), 57 (9). HRMS (EI) for
C25H30SO3: 410.1916. Found: 410.1912.
121.45 MHz, 85% H3PO4) d 54.6, 55.8. IR (CH2Cl2) n 3056, 3003, 2918,
2866, 1598, 1492, 1436, 1374, 1306, 1096, 908, 767, 731, 718, 690,
649, 525 cmꢁ1. MS (%) m/e 538 (Mþ, 9), 336 (9), 321 (100), 289 (46),
273 (52), 237 (84), 217 (45), 205 (33), 91 (26). HRMS (EI) for
C34H35S2P: 538.1918. Found: 538.1919.
4.2.17. S-2,2-Bis(4-chlorophenyl)-1-(2,2,3,3-
tetramethylcyclopropyl)vinyl ethanethioate 5d
A white solid, Mp: 125–127 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
d
0.63 (s, 6H, 2CH3), 0.95 (s, 6H, 2CH3), 1.70 (s, 1H, CH), 2.12 (s, 3H,
CH3), 6.99 (d, J¼11.2 Hz, 2H, Ar), 7.24 (d, J¼11.2 Hz, 6H, Ar). 13C NMR
4.2.12. 2,2,3,3-Tetramethyl-1-(2-phenylprop-1-enyl)cyclopropyl
diphenylphosphinodithioate 2k
(CDCl3, 100 MHz, TMS) d 18.3, 22.9, 25.1, 30.1, 39.9, 127.7, 128.0,
128.4, 131.0, 132.0, 133.4, 133.9, 140.0, 141.0, 152.3, 192.7. IR (CH2Cl2)
The ratio of E/Z¼4:1. A white solid, Mp: 79–81 ꢀC; 1H NMR
n .
2919, 2869, 1698, 1488, 1111, 1090, 1016, 945, 829, 802, 614 cmꢁ1
(CDCl3, 300 MHz, TMS)
d
1.09–1.10 (m, 7H, CH3), 1.43 (s, 7H, CH3),
MS (%) m/e 418 (Mþ, 4), 375 (100), 340 (23), 256 (13), 215 (14), 189
(22), 97 (27), 57 (39), 43 (39). HRMS (EI) for C23H24SOCl2: 418.0925.
Found: 418.0926.
2.00 (s, 3H, CH3), 5.73 (s, 0.24H, CH), 6.08 (s, 0.96H, CH), 6.86–6.89
(m, 2H, Ar), 7.08–7.11 (m, 3H, Ar), 7.26–7.49 (m, 9H, Ar), 7.77–8.24
(m, 5H, Ar). 31P NMR (CDCl3,121.45 MHz, 85% H3PO4)
d 60.5, 60.0. IR
(CH2Cl2)
n
3055, 2987, 2917, 2868, 1436, 1375, 1303, 1097, 1027, 903,
4.2.18. S-2,2-Bis(4-fluorophenyl)-1-(2,2,3,3-
748, 718, 690, 650 cmꢁ1. MS (%) m/e 462 (Mþ, 2), 245 (100), 217 (20),
197 (38), 171 (32), 161 (54), 128 (47), 115 (18), 91 (24). HRMS (EI) for
C28H31S2P: 462.1605. Found: 462.1608.
tetramethylcyclopropyl)vinyl ethanethioate 5e
A white solid, Mp: 112–1114 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
d
0.63 (s, 6H, 2CH3), 0.95 (s, 6H, 2CH3), 1.71 (s, 1H, CH), 2.11 (s, 3H,
CH3), 6.93–6.99 (m, 4H, Ar), 7.02–7.05 (m, 2H, Ar), 7.26–7.31 (m, 2H,
Ar). 13C NMR (CDCl3, 100 MHz, TMS)
18.3, 22.9, 25.1, 30.1, 39.9,
4.2.13. (Deuterium labeling)-1-(2,2-diphenylvinyl)-2,2,3,3-
tetramethylcyclopropyl diphenylphosphinodithioate 2a-D
A white solid, Mp: 124–126 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
d
114.4 (d, JC–F¼17.0 Hz), 114.7 (d, JC–F¼21.0 Hz), 127.5, 131.3 (d, JC–F
¼
8.6 Hz), 132.4 (d, JC–F¼7.8 Hz), 137.8 (d, JC–F¼3.0 Hz), 138.8 (d, JC–F
¼
d
0.38 (s, 3H, CH3), 1.07 (s, 3H, CH3), 1.23 (s, 3H, CH3), 1.48 (s, 3H,
4.1 Hz), 152.6, 162.1 (d, JC–F¼245.2 Hz), 162.4 (d, JC–F¼247.3 Hz),
CH3), 6.20 (s, 0.3H, CH), 6.85–6.87 (m, 2H, Ar), 7.06–7.14 (m, 6H, Ar),
7.25–7.28 (m, 3H, Ar), 7.33–7.42 (m, 5H, Ar), 7.73 (dd, J¼7.2, 12.8 Hz,
2H, Ar), 7.91 (dd, J¼6.8, 13.2 Hz, 2H, Ar). 31P NMR (CDCl3,
192.9. 19F NMR (CDCl3, 282 MHz, CFCl3)
(CH2Cl2)
d
ꢁ113.2, ꢁ114.4. IR
n
3043, 2976, 2947, 2920, 2869, 1698, 1601, 1505, 1451,
1377, 1226, 1156, 1112, 1015, 946, 837, 616, 541 cmꢁ1. MS (%) m/e 386
(Mþ, 3), 343 (100), 313 (7), 259 (18), 246 (19), 201 (16), 141 (11), 109
(16), 91 (4). HRMS (EI) for C23H24SOF2: 386.1516. Found: 386.1512.
121.45 MHz, 85% H3PO4) d
59.3. MS (%) m/e 525 (Mþ, 6.1), 524 (2.6),
308 (100), 292 (18), 275 (26), 260 (19), 234 (45), 224 (78), 217 (31).
4.2.14. S-2,2-Diphenyl-1-(2,2,3,3-tetramethylcyclopropyl)vinyl
ethanethioate 5a
4.2.19. (2,2-Diphenyl-1-(2,2,3,3-tetramethylcyclopropyl)vinyl)
(phenyl)sulfane 8
A white solid, Mp: 92–94 ꢀC; 1H NMR (CDCl3, 300 MHz, TMS)
A colorless oil. 1H NMR (CDCl3, 300 MHz, TMS)
d
0.71 (s, 6H,
2CH3), 0.77 (s, 6H, 2CH3), 1.64 (s, 1H, CH), 7.19–7.44 (m, 15H, Ar). 13
NMR (CDCl3, 75 MHz, TMS) 18.5, 22.7, 25.5, 39.8, 126.3, 127.0,
127.2,127.3,127.8,128.3,130.1,130.8,131.6,133.9,136.0,142.6,143.0,
d
0.63 (s, 6H, 2CH3), 0.93 (s, 6H, 2CH3), 1.80 (s, 1H, CH), 2.10 (s, 3H,
CH3), 7.06–7.09 (m, 2H, Ar), 7.24–7.27 (m, 6H, Ar), 7.31–7.34 (m, 2H,
Ar). 13C NMR (CDCl3, 75 MHz, TMS)
18.3, 22.9, 25.0, 30.1, 39.8,
127.19, 127.23, 127.28, 127.6, 127.8, 129.6, 130.7, 141.8, 143.0, 154.6,
C
d
d
146.8. IR (CH2Cl2) n 3056, 3019, 2978, 2918, 2867, 2729, 1944, 1874,
193.5. IR (CH2Cl2)
n
3056, 2975, 2919, 2867, 1942, 1697, 1492, 1443,
1802, 1581, 1491, 1475, 1442, 1376, 1119, 1025, 734, 697 cmꢁ1. MS (%)
m/e 384 (Mþ, 100), 259 (34), 218 (22), 191 (80), 167 (45), 151 (61),
105 (14), 91 (22), 57 (22). HRMS (EI) for C27H28S: 384.1912. Found:
384.1919.
1376, 1350, 1114, 1075, 947, 757, 698, 619 cmꢁ1. MS (%) m/e 350 (Mþ,
6), 307 (100), 277 (6), 223 (21), 191 (15), 165 (23), 97 (33), 57 (30),
43 (31). HRMS (EI) for C23H26SO: 350.1704. Found: 350.1704.
4.2.15. S-1-(2,2,3,3-Tetramethylcyclopropyl)-2,2-dip-tolylvinyl
ethanethioate 5b
4.2.20. The product mixtures from the reaction of
vinylidenecyclopropane 1a and O,O-diethyl S-hydrogen
phosphorodithioate 9
A white solid, Mp: 101–103 ꢀC; 1H NMR (CDCl3, 400 MHz, TMS)
d
0.63 (s, 6H, 2CH3), 0.93 (s, 6H, 2CH3), 1.81 (s, 1H, CH), 2.11 (s, 3H,
A colorless oil. 1H NMR (CDCl3, 400 MHz, TMS)
d
1.01–1.06 (m,
6H), 3.99–4.09 (m, 4H), 6.38 (s, 1H, CH), 7.24–7.34 (m, 8H, Ar), 7.53–
7.55 (m, 2H, Ar). 31P NMR (CDCl3, 121.45 MHz, 85% H3PO4)
93.84,
93.85, 95.69, 96.12. IR (CH2Cl2) 3058, 2983, 2921, 1494, 1443, 1373,
1158, 1099, 1016, 956, 768, 699, 651, 610 cmꢁ1. MS (%) m/e 460 (Mþ,
CH3), 2.33 (s, 3H, CH3), 2.34 (s, 3H, CH3), 6.95 (d, J¼8.0 Hz, 2H, Ar),
7.05 (d, J¼8.0 Hz, 2H, Ar), 7.06 (d, J¼8.0 Hz, 2H, Ar), 7.20 (d,
d
J¼8.0 Hz, 2H, Ar). 13C NMR (CDCl3, 100 MHz, TMS)
d
18.3, 21.27,
n
21.30, 22.9, 25.0, 30.1, 39.9, 126.2, 127.9, 128.3, 129.5, 130.7, 136.9,

W. Li, M. Shi / Tetrahedron 65 (2009) 6815–6821
6821
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Acknowledgements
We thank the Shanghai Municipal Committee of Science and
Technology (06XD14005, 08dj1400100-2), National Basic Research
Program of China (973)-2009CB825300, and the National Natural
Science Foundation of China (20872162, 20672127, 20821002 and
20732008) and Mr. Jie Sun for X-ray diffraction.
Supplementary data
8. For the synthesis of vinylidenecyclopropanes, please see: (a) Isagawa, K.;
Mizuno, K.; Sugita, H.; Otsuji, Y. J. Chem. Soc., Perkin Trans. 1 1991, 2283–2285
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1H, 13C, 31P and 19F NMR spectra for the corresponding addition
products 3, 5, 8 and 9. This material is available free of charge via
the Internet. Supplementary data associated with this article can be
found in the online version, at doi:10.1016/j.tet.2009.06.090.
Perkin Trans.
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