Rhodium(III)-catalyzed regioselective C-H alkenylation of phenylphosphine sulfides

Article abstract of DOI:10.1021/jo501542b

The regioselective alkenylation at the ortho position of phenylphosphine sulfides using alkenes proceeds efficiently in the presence of a cationic Cp*-rhodium(III) catalyst and an appropriate oxidant. A similar rhodium catalyst also promotes the redox-neutral coupling of the phosphine sulfides with alkynes to afford ortho-alkenylated products.

Full text of DOI:10.1021/jo501542b

Article
pubs.acs.org/joc
Rhodium(III)-Catalyzed Regioselective C−H Alkenylation of
Phenylphosphine Sulfides
Yuki Yokoyama,† Yuto Unoh,† Koji Hirano,† Tetsuya Satoh,*,†,‡ and Masahiro Miura*,†
†Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
‡JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
S
* Supporting Information
ABSTRACT: The regioselective alkenylation at the ortho position of
phenylphosphine sulfides using alkenes proceeds efficiently in the
presence of a cationic Cp*-rhodium(III) catalyst and an appropriate
oxidant. A similar rhodium catalyst also promotes the redox-neutral
coupling of the phosphine sulfides with alkynes to afford ortho-
alkenylated products.
Scheme 1. Rhodium-Catalyzed Regioselective Alkenylation
INTRODUCTION
■
The direct C−H functionalization reactions of arenes and
heteroarenes under transition-metal catalysis have attracted
much attention as powerful synthetic tools because they
provide atom- and step-economical routes to target molecules
from readily available substrates without preactivation by
halogenation or metalation.1 Among such useful trans-
formations, catalytic dehydrogenative alkenylation using
alkenes in the presence of a palladium catalyst and an oxidant,
known as the Fujiwara−Moritani reaction,2 has been developed
and utilized in the synthesis of π-conjugated alkenylarene
molecules. However, in this reaction there is a substantial
problem of forming mixtures of regioisomers of alkenylarenes.
This can be overcome by utilizing a directing group, which is
capable of inducing regioselective C−H alkenylation at the
proximate positions. As such directing groups, oxygen- and
nitrogen-containing substituents including carboxyl, hydroxy,
amide, and pyridyl functions have been widely employed.1 In
addition, phosphorus-containing groups such as phosphinoxy
and phosphine oxide groups have been recently shown to be
applicable. As leading examples, Kim and Lee’s and Moon’s
groups (using palladium catalyst)3 and we (using rhodium or
ruthenium catalyst)4,5 reported P−OH or PO group-directed
regioselective functionalization. In the context of our
continuous studies on rhodium catalysis,1t we succeeded in
finding that phenylphosphine sulfides also undergo catalytic
alkenylation through C−H bond cleavage directed by their P
S group to produce ortho-alkenylated phenylphosphine sulfides
(Scheme 1). Such ortho-substituted phenylphosphine sulfides
have recently attracted attention because of their applicability as
soft and flexible ligands for transition metals.6 In addition, a
relevant ortho-alkenylation using internal alkynes in the
presence of a similar catalyst system is also disclosed herein.
RESULTS AND DISCUSSION
■
In an initial attempt, dicyclohexyl(phenyl)phosphine sulfide
(1a) (0.25 mmol) was treated with butyl acrylate (2a) (2
mmol) under conditions similar to those for the reaction of
phenylphosphine oxides,4a in the presence of [Cp*Rh-
(MeCN)3][SbF6]2 (0.01 mmol) and AgOAc (1 mmol) in o-
dichlorobenzene (3 mL) at 120 °C for 6 h under N2. In
contrast to the oxides, sulfide 1a did not undergo alkenylation
smoothly. Thus, only a trace amount of desired product, butyl
(E)-3-[2-(dicyclohexylphosphorothioyl)phenyl]acrylate (3a),
was formed (entry 1 in Table 1). One of reasons for the
failure is likely due to the thiophilicity of silver. Expectedly, the
use of Cu(OAc)2·H2O (0.5 mmol) in place of AgOAc
significantly improved the reaction efficiency to give 3a in
50% yield (entry 2). It was confirmed that the reaction did not
proceed at all in the absence of the rhodium catalyst (entry 3).
The use of cationic [Cp*Rh(MeCN)3][SbF6]2 is essential for
the reaction: electrically neutral [Cp*RhCl2]2 did not promote
the reaction effectively (entry 4). The yield of 3a was enhanced
to 60% in chlorobenzene (entry 5). The addition of 1,2,3,4-
tetraphenyl- and 1,2,3,4,5-pentaphenyl-1,3-cyclopentadienes
Received: July 11, 2014
Published: July 30, 2014
© 2014 American Chemical Society
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Table 1. Reaction of Dicyclohexyl(phenyl)phosphine Sulfide
(1a) with Butyl Acrylate (2a)
Table 2. Reaction of Phenylphosphine Sulfides 1 with
a
a
Alkenes 2
b
entry
additive
solvent
yield of 3a (%)
c
1
o-C6H4Cl2
o-C6H4Cl2
o-C6H4Cl2
o-C6H4Cl2
C6H5Cl
tr
2
50
d
3
e
0
4
tr
5
6
7
8
60
f
C5H2Ph4
C6H5Cl
62
g
g
g
C5HPh5
C5HPh5
C5HPh5
C6H5Cl
69
diglyme
74 (61)
69 (58)
h
9
diglyme
a
Reaction conditions: 1a (0.25 mmol), 2a (2 mmol), [Cp*Rh-
(MeCN)3][SbF6]2 (0.01 mmol), additive (0.01 mmol), Cu(OAc)2·
H2O (0.5 mmol), in solvent (3 mL) at 120 °C for 8 h under N2, unless
b
otherwise noted. GC yield based on the amount of 1a used. Value in
c
parentheses indicates yield after purification. Using AgOAc (1 mmol)
d
in place of Cu(OAc)2·H2O. Without [Cp*Rh(MeCN)3][SbF6]2.
e
Using [(Cp*RhCl2)2] (0.005 mmol) in place of [Cp*Rh(MeCN)3]-
f
g
[SbF6]2. C5H2Ph4 = 1,2,3,4-tetraphenyl-1,3-cyclopentadiene. C5HPh5
= 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene. With 2a (1 mmol).
h
(0.01 mmol) (C5H2Ph4 and C5HPh5, respectively) slightly
improved the 3a yield (entries 6 and 7). This kind of Cp-ligand
was previously employed for promoting rhodium-catalyzed
oxidative coupling,7 although its exact role was not clear. With
C5HPh5 in diglyme, the best yield of 3a (74%) was obtained
(entry 8). Under these conditions, a comparable yield was still
achieved even when the amount of 2a was reduced to 1 mmol
(entry 9).
Under the optimized reaction conditions, the coupling
reactions of a number of substituted phenyl- and naphthyl-
phosphine sulfides with alkenes were next examined (Table 2).
Treatment of 1a with various acrylate esters 2b−e gave the
corresponding ortho-alkenylated phenylphosphine sulfides in
moderate to good yields (entries 1−5). In some cases,
contamination by trace amounts of 2Z-isomers was observed.
In contrast, the reaction with an acrylamide 2g afforded 3g as a
mixture of 2E- and 2Z-isomers (entry 6). It was found that
styrene (2h) is less reactive than acrylic acid derivatives.
However, the reaction of 1a with 2h proceeded by increasing
the amount of Rh catalyst and extending the reaction time to 30
h to give the stilbene derivative 3h (entry 7).
a
Reaction conditions: 1 (0.25 mmol), 2 (1 mmol), [Cp*Rh-
(MeCN)3][SbF6]2 (0.01 mmol), C5HPh5 (0.01 mmol), Cu(OAc)2·
H2O (0.5 mmol), in diglyme (3 mL) at 120 °C for 8 h under N2,
b
c
1
unless otherwise noted. Determined by H NMR. The reaction was
conducted with [Cp*Rh(MeCN)3][SbF6]2 (0.02 mmol) in the
absence of C5HPh5 for 30 h.
A series of para- and meta-substituted phenylphosphine
sulfides 1b−h underwent the coupling with 2a to produce 3i−o
in 35−74% yields (entries 8−14). In the reaction of
dicyclohexyl(2-naphthyl)phosphine sulfide (1l), alkenylation
took place at the sterically less hindered position to afford a 3-
alkenylated product 3p selectively (entry 15). In addition to
these aryldicyclohexylphosphine sulfides, diisopropyl(phenyl)-
phosphine sulfide (1j) also reacted with 2a to give 3q (entry
16).
A plausible mechanism for the reaction of phenylphosphine
sulfide 1 with alkene 2 is illustrated in Scheme 2. Coordination
of the PS group6d of 1 to a cationic RhIII center and
subsequent ortho-rhodation would occur to form a five-
membered rhodacycle intermediate A. Then, alkene insertion
to form B and β-hydrogen elimination may take place to
produce 3 involving H+ release. The resulting RhI species
would be oxidized by CuII to regenerate RhIII.
To obtain mechanistic insight, a deuterated substrate,
dicyclohexyl(d5-phenyl)phosphine sulfide (1a-d5), was treated
with 2a under standard conditions (Scheme 3a). In the early
stage, considerable contamination by protons at the ortho
positions of recovered 1a-dn as well as at the 6-position of
produced 3a-dn was observed. This result indicates that the
initial C−H(D) bond cleavage step to form A is likely
reversible. This is supported by the observed H−D exchange at
the ortho positions of 1a upon treatment with CD3CO2D in
chlorobenzene in the presence of [Cp*Rh(MeCN)3][SbF6]2
(Scheme 3b). Interestingly, the H−D exchange did not take
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Scheme 2. Plausible Mechanism for the Reaction of 1 with 2
Scheme 4. Reaction of 4 with 2a
Table 3. Reaction of Dicyclohexyl(phenyl)phosphine Sulfide
a
(1a) with 1-Phenyl-1-propyne (6a)
Scheme 3. Investigation for Mechanistic Insights
b
entry
additive
AcOH
solvent
yield of 3a (%)
1
diglyme
C6H5Cl
o-C6H4Cl2
DMF
32
2
AcOH
41
3
AcOH
37
4
AcOH
14
5
AcOH
o-xylene
C6H5Cl
C6H5Cl
C6H5Cl
C6H5Cl
C6H5Cl
C6H5Cl
C6H5Cl
19
6
EtCO2H
1-AdCO2H
PivOH
41
7
35
8
32
9
2,6-Me2C6H3CO2H
CF3CO2H
AcOH
25
10
8
c
11
43
d
12
AcOH
53 (47)
a
Reaction conditions: 1a (0.25 mmol), 6a (0.25 mmol), [Cp*Rh-
(MeCN)3][SbF6]2 (0.01 mmol), acid (1 mmol), in solvent (3 mL) at
120 °C for 3 h under N2, unless otherwise noted. GC yield based on
b
the amount of 6a used. Value in parentheses indicates yield after
c
d
purification. At 100 °C. With 1a (0.38 mmol).
the presence of [Cp*Rh(MeCN)3][SbF6]2 (0.01 mmol) and
AcOH (1 mmol) in diglyme (3 mL) at 120 °C under N2 to
produce dicyclohexyl(2-(1-phenylprop-1-en-2-yl)phenyl)-
phosphine sulfide (7a) in 32% yield (entry 1 in Table 3).
Chlorobenzene was found to be the solvent of choice among
those examined (entries 1−5). The selection of acid was also
important. EtCO2H was as effective as AcOH (entry 6),
although 1-adamantanecarboxylic acid, pivalic acid, 2,6-
dimethylbenzoic acid, and trifluoroacetic acid were less effective
(entries 7−10). At 100 °C, a similar result was obtained (entry
11). Finally, the use of a slightly excess amount of 1a (1.5
equiv) increased the yield of 7a to 53% (entry 12). The NMR
spectra for 7a isolated in entry 12 showed that the alkenyl
moiety of the product has E geometry (E/Z = >99:1).
The ortho-alkenylations of 1a with other alkynes 6 were next
examined. Unsubstituted and substituted diphenylacetylene
6b−e reacted with 1a under similar conditions to afford
products 7b−e (entries 1−4 in Table 4). In the cases with 6b
and 6c, only the E-isomer of 7 was obtained selectively. The
reactions of unsymmetrical alkynes 6f and 6g proceeded
regioselectively to produce 7f and 7g in moderate yields
(entries 5 and 6).
place at all in the presence of neutral RhIII species such as
[Cp*RhCl2]2 and Cp*Rh(OAc)2 (Scheme 3c). Therefore, the
use of a cationic Rh catalyst is essential to facilitate the C−
H(D) bond cleavage step, while it is likely that other steps
including alkene insertion can also be promoted by it.
It was found that alkenylation on an alkenyl C−H bond can
be performed by utilizing the PS directing group. Thus,
treatment of dicyclohexyl(1-phenylethen-1-suppyl)phosphine
sulfide (4) (0.25 mmol) with 2a (1 mmol) in the presence of
[Cp*Rh(MeCN)3][SbF6]2 (0.01 mmol), C5HPh5 (0.01
mmol), and Cu(OAc)2·H2O (0.5 mmol) in diglyme (3 mL)
at 120 °C for 8 h under N2 gave butyl (2E,4Z)-5-
(dicyclohexylphosphorothioyl)-5-phenylpenta-2,4-dienoate (5)
in a moderate yield (Scheme 4).
Recently, we7a,8 and other groups5c,9 reported the Cp*RhIII-
catalyzed ortho-alkenylation using alkynes as alkenyl source
under redox-neutral conditions. Therefore, we applied the
procedure to phenylphosphine sulfides. Expectedly, 1a (0.25
mmol) reacted with 1-phenyl-1-propyne (6a) (0.25 mmol) in
The ortho-alkenylation of 1a with alkynes 6 seems to proceed
through a common rhodacycle intermediate A in Scheme 2.
Alkyne insertion into the C−Rh bond in A and subsequent
protonolysis by AcOH may occur to produce 7 accompanied by
regeneration of an active RhIII species (Scheme 5).
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a
under vacuum, product 3 was isolated by column chromatography on
silica gel using hexane/ethyl acetate (20:1, v/v) as eluent.
Table 4. Reaction of 1a with Alkynes 7
General Procedure for the Reaction of Phenylphosphine
Sulfides with Alkynes. To a 20 mL two-necked flask with a reflux
condenser, a balloon, and a rubber cup were added phenylphosphine
sulfide 1 (0.38 mmol), alkyne 6 (0.25 mmol), [Cp*Rh(MeCN)3]-
[SbF6]2 (0.01 mmol, 8 mg), AcOH (1 mmol, 57 μL), dibenzyl (ca. 30
mg) as internal standard, and chlorobenzene (3 mL). Then, the
resulting mixture was stirred under nitrogen at 120 °C for 3 h. After
cooling, the reaction mixture was extracted with ethyl acetate (100
mL). The organic layer was washed by water (100 mL, three times)
and dried over Na2SO4. After evaporation of the solvent under
vacuum, product 7 was isolated by column chromatography on silica
gel using hexane/ethyl acetate (20:1, v/v) as eluent. Further
purification by gel permeation chromatography (GPC) was performed,
if needed.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
acrylate (3a). Colorless oil, 66 mg (61%); hexane/ethyl acetate
95:5 (v/v, eluent); 1H NMR (400 MHz, CDCl3) δ 0.99 (t, J = 7.3 Hz,
3H), 1.08−2.43 (m, 26H), 4.27 (t, J = 6.5 Hz, 2H), 6.29 (d, J = 15.5
Hz, 1H), 7.47−7.60 (m, 3H), 8.36 (d, J = 15.5 Hz, 1H), 8.39−8.47
(m, 1H); 13C NMR (100 MHz, CDCl3) δ 13.7, 19.2, 25.5 (d, J = 1.5
Hz), 26.32 (d, J = 1.5 Hz), 26.33 (d, J = 2.3 Hz), 26.5 (d, J = 13.3 Hz),
27.4 (d, J = 2.2 Hz), 30.7, 39.7 (d, J = 48.6 Hz), 64.3, 121.6, 127.8 (d, J
= 8.7 Hz), 128.5 (d, J = 62.2 Hz), 129.4 (d, J = 11.3 Hz), 131.3 (d, J =
11.2 Hz), 136.4 (d, J = 9.8 Hz), 137.1 (d, J = 5.9 Hz), 143.5 (d, J = 2.2
Hz), 166.2; 31P{1H} NMR (162 MHz, CDCl3) δ 64.7; HRMS m/z
calcd for C25H38O2PS (M + H+) 433.2325, found 433.2331.
Isobutyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
acrylate (3b). Colorless oil, 65 mg (60%); hexane/ethyl acetate
95:5 (v/v, eluent); 1H NMR (400 MHz, CDCl3) δ 1.03 (d, J = 6.7 Hz,
6H), 1.09−2.43 (m, 23H), 4.06 (d, J = 6.5 Hz, 2H), 6.30 (d, J = 15.6
Hz, 1H), 7.47−7.63 (m, 3H), 8.33−8.48 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 19.2, 25.6 (d, J = 1.2 Hz), 26.36 (d, J = 13.5 Hz),
26.37 (d, J = 2.7 Hz), 26.5 (d, J = 13.8 Hz), 27.4 (d, J = 2.1 Hz), 27.9,
39.8 (d, J = 48.5 Hz), 71.0, 121.6, 127.9 (d, J = 8.5 Hz), 128.6 (d, J =
60.3 Hz), 129.4 (d, J = 11.2 Hz), 131.5 (d, J = 2.7 Hz), 136.4 (d, J =
9.5 Hz), 137.2 (d, J = 6.1 Hz), 143.5 (d, J = 2.3 Hz), 166.2; 31P{1H}
NMR (162 MHz, CDCl3) δ 64.5; HRMS m/z calcd for C25H38O2PS
(M + H+) 433.2325, found 433.2351.
a
Reaction conditions: 1a (0.38 mmol), 6 (0.25 mmol), [Cp*Rh-
(MeCN)3][SbF6]2 (0.01 mmol), AcOH (1 mmol), in chlorobenzene
(3 mL) at 120 °C for 3 h under N2. Determined by H NMR.
b
1
Scheme 5. Possible Pathway for the Reaction of 1a with 6
CONCLUSIONS
tert-Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
■
acrylate (3c). (E:Z = 96:4) Yellow oil, 79 mg (73%); hexane/ethyl
We have demonstrated that the rhodium-catalyzed ortho-
alkenylation of phenylphosphine sulfides takes place through
PS group-directed C−H bond cleavage. The ortho-
alkenylated phenylphosphine sulfides can also be prepared via
the redox-neutral coupling with alkynes.
1
acetate 95:5 (v/v, eluent); H NMR (400 MHz, CDCl3) δ 1.09−1.41
(m, 10H), 1.58 (s, 9H), 1.61−2.43 (m, 12H), 6.02 (d, J = 12.0 Hz, 1H,
Z), 6.19 (d, J = 15.5 Hz, 1H), 7.40−7.63 (m, 3H), 8.23 (d, J = 15.5 Hz,
1H), 8.38−8.55 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 25.6 (d, J =
1.5 Hz), 26.4 (d, J = 3.0 Hz), 26.5 (d, J = 13.2 Hz), 26.6 (d, J = 13.9
Hz), 27.5 (d, J = 2.5 Hz), 28.2, 39.8 (d, J = 48.4 Hz), 81.0, 123.8, 127.7
(d, J = 8.6 Hz), 128.4 (d, J = 60.5 Hz), 129.2 (d, J = 11.3 Hz), 131.4
(d, J = 2.5 Hz), 136.7 (d, J = 10.0 Hz), 137.2 (d, J = 5.8 Hz), 142.7 (d,
J = 2.5 Hz), 165.3; 31P{1H} NMR (162 MHz, CDCl3) δ 63.5 (Z), 64.8
(E); HRMS m/z calcd for C25H38O2PS (M + H+) 433.2325, found
433.2328.
EXPERIMENTAL SECTION
■
1
General. H and 13C NMR spectra were recorded at 400 and 100
MHz for CDCl3 solutions. HRMS data were obtained by EI using a
double focusing mass spectrometer, unless noted otherwise. GC
analysis was carried out using a silicon OV-17 column (i.d. 2.6 mm ×
1.5 m). GC−MS analysis was carried out using a CBP-1 capillary
column (i.d. 0.25 mm × 25 m). The structures of all products listed
below were unambiguously determined by 1H and 13C NMR with the
aid of NOE, COSY, HMQC, and HMBC experiments.
Cyclohexyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
acrylate (3d). Pale yellow oil, 65 mg (65%); hexane/ethyl acetate
95 (v/v, eluent); 1H NMR (400 MHz, CDCl3) δ 1.07−2.45 (m, 32H),
4.98 (tt, J = 3.5, 8.6 Hz, 1H), 6.29 (d, J = 15.6 Hz, 1H), 7.47−7.63 (m,
3H), 8.36 (d, J = 15.5 Hz, 1H), 8.40−8.50 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 23.5, 25.4, 25.6 (d, J = 1.0 Hz), 26.38 (d, J = 2.5 Hz),
26.39 (d, J = 13.0 Hz), 26.5 (d, J = 13.0 Hz), 27.5 (d, J = 2.0 Hz), 31.6,
39.8 (d, J = 48.5 Hz), 72.9, 122.2, 127.7 (d, J = 8.5 Hz), 128.5 (d, J =
60.5 Hz), 129.4 (d, J = 11.1 Hz), 131.5 (d, J = 2.7 Hz), 136.5 (d, J =
9.5 Hz), 137.1 (d, J = 6.5 Hz), 143.2 (d, J = 2.8 Hz), 165.6; 31P{1H}
NMR (162 MHz, CDCl3) δ 64.7; HRMS m/z calcd for C27H40O2PS
(M + H+) 459.2481, found 459.2495.
Phosphine sulfides 1a−j and 410,11 and alkynes 6b−e12 and 6g13
were prepared according to published procedures. All starting
materials and reagents were commercially available.
General Procedure for the Reaction of Phenylphosphine
Sulfides with Alkenes. To a 20 mL two-necked flask with a reflux
condenser, a balloon, and a rubber cup were added phenylphosphine
sulfide 1 (0.25 mmol), alkene 2 (1 mmol), [Cp*Rh(MeCN)3][SbF6]2
(0.01 mmol, 8 mg), C5HPh5 (0.01 mmol, 5 mg), Cu(OAc)2·H2O (0.5
mmol, 100 mg), dibenzyl (ca. 30 mg) as internal standard, and diglyme
(3 mL). Then, the resulting mixture was stirred under nitrogen at 120
°C for 8 h. After cooling, the reaction mixture was extracted with ethyl
acetate (100 mL). The organic layer was washed by water (100 mL,
three times) and dried over Na2SO4. After evaporation of the solvent
Ethyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
acrylate (3e). (E:Z = 98:2) Yellow oil, 42 mg (42%); hexane/ethyl
1
acetate 95:5 (v/v, eluent); H NMR (400 MHz, CDCl3) δ 1.09−2.44
(m, 25H), 4.32 (q, J = 7.1 Hz, 2H), 6.11 (d, J = 12.0 Hz, 1H, Z), 6.29
(d, J = 15.5 Hz, 1H), 7.48−7.63 (m, 3H), 8.370 (d, J = 15.6 Hz, 1H),
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8.371−8.48 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 14.3, 25.6 (d, J
= 1.4 Hz), 26.3 (d, J = 11.7 Hz), 26.4 (d, J = 2.9 Hz), 26.5 (d, J = 11.6
Hz), 27.4 (d, J = 2.8 Hz), 39.8 (d, J = 48.6 Hz), 60.8, 121.6, 127.9 (d, J
= 8.5 Hz), 128.6 (d, J = 60.2 Hz), 129.4 (d, J = 11.0 Hz), 131.5 (d, J =
2.5 Hz), 136.5 (d, J = 9.7 Hz), 137.2 (d, J = 6.6 Hz), 143.7 (d, J = 2.8
Hz), 166.3; 31P{1H} NMR (162 MHz, CDCl3) δ 64.7; HRMS m/z
calcd for C23H34O2PS (M + H+) 405.2012, found 405.2024.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)-5-methoxy-
phenyl)acrylate (3j). (E:Z = 93:7) Pale yellow oil, 41 mg (35%);
hexane/ethyl acetate 95:5 (v/v, eluent); 1H NMR (400 MHz, CDCl3)
δ 0.98 (t, J = 7.4 Hz, 3H), 1.09−2.37 (m, 26H), 3.87 (s, 3H), 4.27 (t, J
= 6.5 Hz, 2H), 6.10 (d, J = 12.0 Hz, 1H, Z), 6.27 (d, J = 15.5 Hz, 1H),
7.01 (dd, J = 2.5, 8.7 Hz, 1H), 7.06 (dd, J = 3.0, 3.1 Hz, 1H), 8.32 (d, J
= 14.4 Hz, 1H), 8.35 (d, J = 13.5 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 13.7, 19.7, 25.6 (br), 26.37 (d, J = 2.5 Hz), 26.39 (d, J = 14.1
Hz), 26.5 (d, J = 14.2 Hz), 27.4 (d, J = 2.1 Hz), 30.8, 39.8 (d, J = 49.3
Hz), 55.4, 64.7, 113.8 (d, J = 9.5 Hz), 114.2 (d, J = 12.2 Hz), 119.5 (d,
J = 65.8 Hz), 121.8, 138.6 (br), 138.7, 143.6 (d, J = 2.0 Hz), 161.9 (d, J
= 2.7 Hz), 166.2; 31P{1H} NMR (162 MHz, CDCl3) δ 61.8 (Z), 63.4
(E); HRMS m/z calcd for C26H40O3PS (M + H+) 463.2430, found
463.2438.
Butyl (E)-3-(5-Chloro-2-(dicyclohexylphosphorothioyl)-
phenyl)acrylate (3k). (E:Z = 97:3) Colorless oil, 45 mg (38%);
hexane/ethyl acetate 90:10 (v/v, eluent); 1H NMR (400 MHz,
CDCl3) δ 0.99 (t, J = 7.4 Hz, 3H), 1.08−2.40 (m, 26H), 4.27 (t, J =
6.5 Hz, 2H), 6.15 (d, J = 12.0 Hz, 1H, Z), 6.31 (d, J = 15.6 Hz, 1H),
7.44−7.56 (m, 2H), 8.26 (d, J = 15.6 Hz, 1H), 8.39 (dd, J = 8.4, 13.7
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 13.7, 19.3, 25.5 (d, J = 1.1
Hz), 26.3 (d, J = 14.5 Hz), 26.4 (overlapped), 26.5 (d, J = 13.9 Hz),
27.4 (d, J = 2.1 Hz), 30.8, 39.8 (d, J = 48.7 Hz), 64.9, 122.9, 127.2 (d, J
= 60.5 Hz), 127.7 (d, J = 9.0 Hz), 129.3 (d, J = 11.8 Hz), 138.1 (d, J =
3.4 Hz), 138.3 (d, J = 10.9 Hz), 138.6 (d, J = 7.0 Hz), 142.2 (d, J = 2.0
Hz), 165.9; 31P{1H} NMR (162 MHz, CDCl3) δ 64.7; HRMS m/z
calcd for C25H37O2ClPS (M + H+) 467.1935, found 467.1944.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)-4-methyl-
phenyl)acrylate (3l). Colorless oil, 82 mg (74%); hexane/ethyl
acetate 95:5 (v/v, eluent); 1H NMR (400 MHz, CDCl3) δ 0.99 (t, J =
7.4 Hz, 3H), 1.09−2.40 (m, 26H), 2.43 (s, 3H), 4.26 (t, J = 6.5 Hz,
2H), 6.28 (d, J = 15.5 Hz, 1H), 7.31 (d, J = 7.8 Hz, 1H), 7.48 (dd, J =
4.5, 7.8 Hz, 1H), 8.25 (d, J = 16.0 Hz, 1H), 8.29 (d, J = 16.2 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 13.7, 19.3, 21.5, 25.6 (d, J = 1.1 Hz),
Phenyl (E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-
acrylate (3f). (E:Z = 96:4) Yellow oil, 33 mg (30%); hexane/ethyl
1
acetate 95:5 (v/v, eluent); H NMR (400 MHz, CDCl3) δ 1.08−1.42
(m, 10H), 1.58−1.78 (m, 6H), 1.80−1.91 (m, 2H), 2.00−2.11 (m,
2H), 2.23−2.42 (m, 2H), 6.30 (d, J = 11.9 Hz, 1H, Z), 6.49 (d, J =
15.5 Hz, 1H), 7.18−7.24 (m, 2H), 7.28−7.31 (m, 1H), 7.40−7.48 (m,
2H), 7.52−7.61 (m, 2H), 7.62−7.72 (m, 2H), 8.32−8.45 (m, 1H),
8.65 (d, J = 15.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 25.6 (d, J =
1.0 Hz), 26.39 (d, J = 13.5 Hz), 26.41 (d, J = 2.7 Hz), 26.5 (d, J = 13.9
Hz), 27.2 (d, J = 2.6 Hz), 39.8 (d, J = 48.6 Hz), 120.3, 121.5, 126.0,
128.1 (d, J = 8.7 Hz), 128.8 (d, J = 59.4 Hz), 129.5, 129.8 (d, J = 11.1
Hz), 131.5 (d, J = 2.4 Hz), 136.3 (br), 137.1 (br), 145.8 (d, J = 2.8
Hz), 150.7, 164.9; 31P{1H} NMR (162 MHz, CDCl3) δ 61.7 (Z), 64.2
(E); HRMS m/z calcd for C27H34O2PS (M + H+) 453.2012, found
453.2011.
(E)-3-(2-(Dicyclohexylphosphorothioyl)phenyl)-N,N-dime-
thylacrylamide (3g). (E:Z = 74:26) Yellow oil, 30 mg (30%);
hexane/ethyl acetate 50:50 (v/v, eluent); 1H NMR (400 MHz,
CDCl3) δ 1.10−1.63 (m, 13H), 1.65−2.13 (m, 7H), 2.23−2.39 (m,
2H, Z), 2.39−2.51 (m, 2H, E), 2.88 (s, 3H, Z), 2.90 (s, 3H, Z), 3.12 (s,
3H, E), 3.20 (s, 3H, E), 6.20 (d, J = 12.3 Hz, 1H, Z), 6.72 (d, J = 14.9
Hz, 1H, E), 7.36−7.43 (m, 3H, Z), 7.47−7.55 (m, 3H, E), 7.50 (d, J =
11.5 Hz, 1H, Z), 7.83−7.97 (m, 1H, Z), 8.16 (d, J = 15.0 Hz, 1H, E),
8.48−8.70 (m, 1H, E); 13C NMR (100 MHz, CDCl3) δ 25.59 (d, J =
1.3 Hz, E), 25.64 (d, J = 1.3 Hz, Z), 26.1 (br, Z), 26.2 (d, J = 13.6 Hz,
E), 26.41 (d, J = 13.1 Hz, overlapped, Z), 26.43 (d, J = 2.6 Hz, E), 26.5
(d, J = 13.6 Hz, overlapped), 27.7 (d, J = 2.3 Hz, E), 34.5 (Z), 36.0
(E), 37.4 (E), 37.7 (Z), 39.4 (d, J = 48.2 Hz, E), 39.9 (d, J = 49.1 Hz,
Z), 121.5 (E), 124.1 (Z), 125.8 (d, J = 62.7 Hz, Z), 127.7 (d, J = 5.7
Hz, E), 127.8 (d, J = 10.6 Hz, Z), 128.5 (d, J = 60.7 Hz, E), 128.9 (d, J
= 11.3 Hz, E), 130.1 (d, J = 9.1 Hz, Z), 131.1 (d, J = 2.6 Hz, Z), 131.3
(d, J = 2.6 Hz, E), 133.5 (br, Z), 134.8 (d, J = 2.9 Hz, Z), 137.1 (d, J =
10.3 Hz, E), 137.9 (d, J = 6.5 Hz, E), 140.5 (br, Z), 141.6 (d, J = 2.0
Hz, E), 165.8 (E), 168.1 (Z); 31P{1H} NMR (162 MHz, CDCl3) δ
60.8 (Z), 66.3 (E); HRMS m/z calcd for C23H35NOPS (M + H+)
404.2171, found 404.2175.
26.4 (d, J = 13.9 Hz), 26.46 (d, J = 2.7 Hz), 26.54 (d, J = 13.8 Hz),
27.7 (d, J = 2.4 Hz), 30.8, 39.9 (d, J = 48.5 Hz), 64.6, 120.8, 127.7 (d, J
= 8.9 Hz), 128.5 (d, J = 60.1 Hz), 132.2 (d, J = 2.6 Hz), 133.8 (d, J =
6.1 Hz), 137.4 (d, J = 10.0 Hz), 140.0 (d, J = 48.9 Hz), 143.3 (d, J =
42.2 Hz), 166.4; 31P{1H} NMR (162 MHz, CDCl3) δ 64.5; HRMS m/
z calcd for C26H40O2PS (M + H+) 447.2481, found 447.2510.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)-4-methoxy-
phenyl)acrylate (3m). (E:Z = 97:3) Purple oil, 66 mg (57%);
hexane/ethyl acetate 90:10 (v/v, eluent); 1H NMR (400 MHz,
CDCl3) δ 0.99 (t, J = 7.4 Hz, 3H), 1.08−1.78 (m, 20H), 1.80−1.92
(m, 2H), 1.99−2.11 (m, 2H), 2.23−2.45 (m, 2H), 3.90 (s, 3H), 4.25
(t, J = 6.5 Hz, 2H), 6.07 (d, J = 11.9 Hz, 1H, Z), 6.24 (d, J = 15.4 Hz,
1H), 7.00 (dd, J = 2.0, 8.5 Hz, 1H), 7.56 (dd, J = 3.6, 5.0 Hz, 1H), 8.13
(dd, J = 2.6, 15.8 Hz, 1H), 8.19 (d, J = 15.5 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 13.7, 19.3, 25.6 (d, J = 1.2 Hz), 26.36 (d, J = 13.6 Hz),
26.40 (d, J = 3.1 Hz), 26.5 (d, J = 13.7 Hz), 27.8 (d, J = 2.3 Hz), 30.8,
40.1 (d, J = 48.2 Hz), 55.6, 64.6, 117.6 (d, J = 5.0 Hz), 119.3, 121.7 (d,
J = 11.6 Hz), 128.7 (d, J = 6.3 Hz), 129.2 (d, J = 10.1 Hz), 131.1 (d, J
= 58.8 Hz), 142.6 (d, J = 2.1 Hz), 160.6 (d, J = 13.3 Hz), 166.6;
31P{1H} NMR (162 MHz, CDCl3) δ 64.5 (Z), 66.4 (E); HRMS m/z
(E)-Dicyclohexyl(2-styrylphenyl)phosphine Sulfide (3h). (E:Z
= 93:7) Yellow oil, 33 mg (32%); hexane/ethyl acetate 90:10 (v/v,
1
eluent); H NMR (400 MHz, CDCl3) δ 1.06−1.51 (m, 10H), 1.58−
2.46 (m, 12H), 6.73 (d, J = 12.3 Hz, 1H, Z), 6.90 (d, J = 15.9 Hz, 1H),
7.29−7.66 (m, 8H), 7.94 (d, J = 15.6 Hz, 1H), 8.22 (dd, J = 7.8, 14.1
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 25.6 (br), 26.4 (d, J = 2.7
Hz), 26.5 (d, J = 6.5 Hz), 26.6 (d, J = 6.5 Hz), 27.0 (d, J = 2.0 Hz),
39.4 (d, J = 48.9 Hz), 126.4 (d, J = 63.0 Hz), 127.0, 127.2 (d, J = 11.2
Hz), 127.9 (d, J = 9.0 Hz), 128.0 (d, J = 3.9 Hz), 128.2, 129.0, 131.4
(d, J = 2.7 Hz), 132.2, 135.3, 137.1, 141.2 (d, J = 5.8 Hz); 31P{1H}
NMR (162 MHz, CDCl3) δ 63.2 (E), 65.7 (Z); HRMS m/z calcd for
C26H34PS (M + H+) 409.2113, found 409.2137.
calcd for C26H40O3PS (M + H+) 463.2430, found 463.2442.
Butyl (E)-3-(3-(Dicyclohexylphosphorothioyl)-[1,1′-biphen-
yl]-4-yl)acrylate (3n). (E:Z = 98:2) Pale yellow oil, 95 mg (74%);
hexane/ethyl acetate 95:5 (v/v, eluent);1H NMR (400 MHz, CDCl3)
δ 1.00 (d, J = 7.4 Hz, 3H), 1.11−2.48 (m, 26H), 4.28 (t, J = 6.5 Hz,
2H), 6.15 (d, J = 12.0 Hz, 1H, Z), 6.36 (d, J = 15.6 Hz, 1H), 7.36−
7.80 (m, 7H), 8.35 (d, J = 15.6 Hz, 1H), 8.75 (d, J = 14.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.7, 19.3, 25.6 (br), 26.4 (d, J = 13.3
Hz), 26.5 (br), 26.6 (d, J = 13.3 Hz), 27.6 (d, J = 2.1 Hz), 30.8, 39.9
(d, J = 48.3 Hz), 64.7, 121.3, 127.1, 128.2, 128.3 (d, J = 9.0 Hz), 129.0,
129.3 (d, J = 58.9 Hz), 129.6 (d, J = 2.7 Hz), 135.3 (d, J = 11.1 Hz),
135.5 (d, J = 5.7 Hz), 139.2, 142.0 (d, J = 11.0 Hz), 143.0 (d, J = 2.3
Hz), 166.4; 31P{1H} NMR (162 MHz, CDCl3) δ 65.4; HRMS m/z
calcd for C31H42O2PS (M + H+) 509.2638, found 509.2640.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)-5-methyl-
phenyl)acrylate (3i). (E:Z = 98:2) Colorless oil, 54 mg (48%);
hexane/ethyl acetate 95:5 (v/v, eluent); 1H NMR (400 MHz, CDCl3)
δ 0.98 (t, J = 7.4 Hz, 3H), 1.07−2.38 (m, 26H), 2.41 (s, 3H), 4.26 (t, J
= 6.5 Hz, 2H), 6.09 (d, J = 12.0 Hz, 1H, Z), 6.28 (d, J = 15.5 Hz, 1H),
7.32 (d, J = 8.0 Hz, 1H), 7.37 (d, J = 5.0 Hz, 1H), 8.29 (dd, J = 8.0,
14.1 Hz, 1H), 8.34 (d, J = 16.3 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 13.7, 19.3, 21.2, 25.6 (d, J = 1.2 Hz), 26.39 (d, J = 2.6 Hz),
26.40 (d, J = 13.8 Hz), 26.5 (d, J = 13.8 Hz), 27.4 (d, J = 2.1 Hz), 30.8,
40.5 (d, J = 48.8 Hz), 64.6, 121.4, 125.6 (d, J = 62.3 Hz), 128.7 (d, J =
8.9 Hz), 130.3 (d, J = 11.5 Hz), 136.7 (d, J = 9.5 Hz), 137.0 (d, J = 6.4
Hz), 141.9 (d, J = 2.6 Hz), 143.8 (d, J = 2.5 Hz), 166.4; 31P{1H} NMR
(162 MHz, CDCl3) δ 64.1; HRMS m/z calcd for C26H40O2PS (M +
H+) 447.2481, found 447.2485.
Butyl (E)-3-(2-(Dicyclohexylphosphorothioyl)-4-(trifluoro-
methyl)phenyl)acrylate (3o). (E:Z = 93:7) Colorless oil, 52 mg
7653
dx.doi.org/10.1021/jo501542b | J. Org. Chem. 2014, 79, 7649−7655

The Journal of Organic Chemistry
Article
1
(41%); hexane/ethyl acetate 95:5 (v/v, eluent); H NMR (400 MHz,
CDCl3) δ 0.99 (t, J = 7.4 Hz, 3H), 1.09−2.44 (m, 26H), 4.29 (t, J =
6.6 Hz, 2H), 6.20 (d, J = 12.0 Hz, 1H, Z), 6.36 (d, J = 15.6 Hz, 1H),
7.67 (dd, J = 3.6, 8.0 Hz, 1H), 7.75 (d, J = 8.1 Hz, 1H), 8.31 (d, J =
15.6 Hz, 1H), 8.75 (d, J = 13.9 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 13.7, 19.3, 25.5 (d, J = 1.4 Hz), 26.3 (d, J = 13.3 Hz), 26.4
(d, J = 3.0 Hz), 26.5 (d, J = 13.9 Hz), 27.5 (d, J = 2.1 Hz), 30.8, 39.8
(d, J = 48.3 Hz), 65.0, 123.5 (q, J = 271.1 Hz), 123.7, 128.1−128.27
(m), 128.33 (d, J = 8.2 Hz), 130.5 (d, J = 58.1 Hz), 131.3 (dq, J = 11.2,
33.1 Hz), 133.3−133.6 (m), 140.5 (d, J = 3.6 Hz), 142.2 (d, J = 1.4
Hz), 165.8; 31P{1H} NMR (162 MHz, CDCl3) δ 63.7 (Z), 65.4 (E);
HRMS m/z calcd for C26H37O2 F3PS (M + H+) 501.2198, found
501.2211.
8.65 (ddd, J = 1.9, 8.5, 15.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
25.4, 26.2 (br, overlapped), 26.4, 27.6 (d, J = 2.6 Hz), 37.8 (d, J = 47.5
Hz), 127.4, 127.6 (d, J = 11.4 Hz), 128.1 (d, J = 61.4 Hz), 128.2,
128.4, 128.7, 129.4, 130.2, 130.8 (d, J = 2.7 Hz), 131.5, 133.5 (d, J =
9.4 Hz), 136.7, 137.7 (d, J = 11.6 Hz), 138.7, 142.9 (d, J = 2.6 Hz),
144.4 (d, J = 7.0 Hz); 31P{1H} NMR (162 MHz, CDCl3) δ 69.7;
HRMS m/z calcd for C32H38PS (M + H+) 485.2426, found 485.2433.
(E)-(2-(1,2-Bis(4-chlorophenyl)vinyl)phenyl)dicyclohexyl-
phosphine Sulfide (7c). Mp 192−193 °C (yellow solid), 37 mg
1
(27%); hexane/ethyl acetate 95:5 (v/v, eluent); H NMR (400 MHz,
CDCl3) δ 0.42−1.54 (m, 13H), 1.57−2.16 (m, 9H), 6.57 (s, 1H),
7.05−7.14 (m, 4H), 7.20−7.26 (m, 4H), 7.29−7.35 (m, 1H), 7.46−
7.57 (m, 2H), 8.49−8.63 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
25.5, 26.4 (br, overlapped), 27.5 (d, J = 2.1 Hz), 38.3 (d, J = 49.9 Hz),
127.8 (d, J = 11.2 Hz), 128.2 (d, J = 61.3 Hz), 128.8, 129.0, 130.56,
130.61, 130.9 (d, J = 2.7 Hz), 131.6, 133.3, 133.4 (d, J = 3.3 Hz),
134.4, 134.8, 137.1, 137.3 (d, J = 11.0 Hz), 142.2 (d, J = 1.4 Hz), 144.4
(d, J = 6.5 Hz); 31P{1H} NMR (162 MHz, CDCl3) δ 68.2; HRMS m/z
calcd for C32H36Cl2PS (M + H+) 553.1647, found 553.1646.
(E)-(2-(1,2-Bis(4-methoxyphenyl)vinyl)phenyl)dicyclohexyl-
phosphine Sulfide (7d). (E:Z = 85:15) White solid, 18 mg (13%);
hexane/ethyl acetate 90:10 (v/v, eluent); 1H NMR (400 MHz,
CDCl3) δ 0.21−1.52 (m, 16H), 1.60−2.10 (m, 6H), 3.72 (s, 3H, Z),
3.81 (s, 6H, E), 3.83 (s, 3H, Z), 6.46 (s, 1H, E), 6.58−6.65 (m, 2H, Z),
6.74−6.84 (m, 4H, E), 6.88−6.94 (m, 2H, Z), 7.04−7.17 (m, 4H, E),
7.31−7.35 (m, 1H, E), 7.32−7.40 (m, 2H, Z), 7.44−7.53 (m, 2H, E),
7.53−7.60 (m, 2H, Z), 7.66−7.75 (m, 1H, Z), 8.56−8.69 (m, 1H, E),
8.69−8.79 (m, 1H, Z); 13C NMR (100 MHz, CDCl3) δ 24.5 (br), 25.4
(br, overlapped), 26.7 (d, J = 2.6 Hz), 36.6 (br), 54.2 (overlapped),
54.3 (E), 54.5 (Z), 112.6 (Z), 112.8 (E), 113.1 (E), 113.3 (Z), 126.3
(d, J = 11.3 Hz, E), 126.6 (d, J = 11.2 Hz, Z), 126.9 (Z), 127.1 (d, J =
61.8 Hz, E), 127.2 (d, J = 60.1 Hz, Z), 127.8 (Z), 127.9 (Z), 128.4 (E),
128.8 (E), 129.5 (Z), 129.6 (E), 129.7 (d, J = 2.6 Hz, E), 129.9 (E),
130.38 (E), 130.42 (Z), 130.6 (d, J = 2.7 Hz, Z), 132.2 (d, J = 9.5 Hz,
Z), 132.4 (d, J = 9.4 Hz, E), 136.6 (d, J = 10.8 Hz, E), 137.1 (d, J =
10.7 Hz, Z), 137.9 (Z), 139.6 (E), 140.3 (d, J = 6.5 Hz, Z), 144.1 (d, J
= 7.1 Hz, E), 157.7 (E), 158.0 (Z), 158.28 (Z), 158.33 (E); 31P{1H}
NMR (162 MHz, CDCl3) δ 67.9 (Z), 69.7 (E); HRMS m/z calcd for
C34H42O2PS (M + H+) 545.2638, found 545.2636.
(E)-Dicyclohexyl(2-(1,2-di-p-tolylvinyl)phenyl)phosphine
Sulfide (7e). (E:Z = 76:24) White solid, 17 mg (13%); hexane/ethyl
acetate 90:10 (v/v, eluent); 1H NMR (400 MHz, CDCl3) δ 0.26−1.53
(m, 16H), 1.59−1.91 (m, 6H), 2.23 (s, 3H, Z), 2.33 (s, 3H, E), 2.35 (s,
3H, E), 2.38 (s, 3H, Z), 6.54 (s, 1H, E), 6.73−6.82 (m, 2H, Z), 6.82−
6.94 (m, 1H, E), 7.00−7.12 (m, 6H), 7.15−7.23 (m, 1H), 7.31−7.40
(m, 1H), 7.44−7.59 (m, 2H), 8.59−8.68 (m, 1H, E), 8.68−8.79 (m,
1H, Z); 13C NMR (100 MHz, CDCl3) δ 21.2 (d, J = 2.9 Hz, Z), 21.4
(d, J = 2.6 Hz, E), 25.5 (br), 25.6 (br), 26.4 (br), 26.6 (br), 27.8 (br),
37.9 (br), 127.0 (Z), 127.5 (d, J = 11.4 Hz, E), 127.8 (d, J = 11.3 Hz,
Z), 128.26 (d, J = 61.6 Hz, E), 128.31 (d, J = 61.1 Hz, Z), 129.1 (Z),
129.2 (E), 129.5 (E), 129.6 (E), 129.7 (Z), 129.8 (Z), 130.2 (E),
130.86 (d, J = 2.7 Hz, E), 130.93 (E), 131.0 (Z), 131.7 (d, J = 2.7 Hz,
Z), 131.8 (Z), 133.27 (Z), 133.34 (d, J = 3.4 Hz, Z), 133.6 (d, J = 9.4
Hz, E), 134.1 (E), 136.2 (E), 137.4 (E), 137.75 (Z), 137.83 (d, J =
10.7 Hz, E), 138.15 (E), 138.24 (d, J = 11.2 Hz, Z), 140.7 (Z), 140.9
(d, J = 1.6 Hz, Z), 141.3 (d, J = 6.8 Hz, Z), 142.1 (d, J = 1.4 Hz, E),
145.1 (d, J = 7.0 Hz, E); 31P{1H} NMR (162 MHz, CDCl3) δ 69.9
(E), 68.0 (Z); HRMS m/z calcd for C34H42PS (M + H+) 513.2739,
found 513.2737.
Butyl (E)-3-(3-(Dicyclohexylphosphorothioyl)naphthalen-2-
yl)acrylate (3p). (E:Z = 97:3) Mp 135−136 °C (pale yellow
solid), 60 mg (49%); hexane/ethyl acetate 95:5 (v/v, eluent); 1H
NMR (400 MHz, CDCl3) δ 1.00 (t, J = 7.4 Hz, 3H), 1.07−2.51 (m,
26H), 4.30 (t, J = 6.5 Hz, 2H), 6.23 (d, J = 11.9 Hz, 1H, Z), 6.43 (d, J
= 15.4 Hz, 1H), 7.50−7.70 (m, 2H), 7.78−8.10 (m, 3H), 8.32 (d, J =
15.4 Hz, 1H), 9.06 (d, J = 16.4 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 13.7, 19.3, 25.6 (d, J = 1.3 Hz), 26.4 (d, J = 14.3 Hz), 26.5
(d, J = 14.1 Hz), 26.6 (d, J = 2.5 Hz), 28.0 (d, J = 2.2 Hz), 30.8, 39.9
(d, J = 48.5 Hz), 64.7, 121.7, 126.8 (d, J = 61.1 Hz), 127.69 (d, J = 8.7
Hz), 127.74, 127.9, 128.7, 129.1, 132.7 (d, J = 12.3 Hz), 132.8 (d, J =
6.2 Hz), 134.0 (d, J = 2.2 Hz), 139.5 (d, J = 9.5 Hz), 143.9, 166.3;
31P{1H} NMR (162 MHz, CDCl3) δ 65.2 (Z), 65.8 (E); HRMS m/z
calcd for C29H40O2PS (M + H+) 483.2481, found 483.2497.
Butyl (E)-3-(2-(Diisopropylphosphorothioyl)phenyl)acrylate
(3q). (E:Z = 97:3) Pale yellow oil, 53 mg (61%); hexane/ethyl acetate
1
95:5 (v/v, eluent); H NMR (400 MHz, CDCl3) δ 0.90 (dd, J = 7.0,
18.1 Hz, 6H), 0.99 (t, J = 7.4 Hz, 3H), 1.35 (dd, J = 6.7, 17.5 Hz, 6H),
1.47 (sext, J = 7.3 Hz, 2H), 1.72 (quin, J = 6.6 Hz, 2H), 2.55−2.72 (m,
2H), 4.25 (t, J = 6.5 Hz, 2H), 6.09 (d, J = 12.0 Hz, 1H, Z), 6.33 (d, J =
15.5 Hz, 1H), 7.49−7.64 (m, 3H), 8.40 (d, J = 15.6 Hz, 1H), 8.47 (m,
1H); 13C NMR (100 MHz, CDCl3) δ 13.7, 17.3 (d, J = 1.9 Hz), 17.7
(d, J = 1.3 Hz), 19.2, 29.8 (d, J = 49.1 Hz), 30.7, 64.8, 121.6, 127.9 (d,
J = 8.7 Hz), 129.2 (d, J = 60.9 Hz), 129.5 (d, J = 11.2 Hz), 131.6 (d, J
= 2.4 Hz), 136.3 (d, J = 2.5 Hz), 136.9 (d, J = 7.1 Hz), 143.1 (d, J =
2.6 Hz), 166.4; 31P{1H} NMR (162 MHz, CDCl3) δ 72.6; HRMS m/z
calcd for C19H30O2PS (M + H+) 353.1699, found 353.1706.
Butyl (2E,4Z)-5-(Dicyclohexylphosphorothioyl)-5-phenyl-
penta-2,4-dienoate (5). Mp 143−144 °C (white solid), 30 mg
1
(26%); hexane/ethyl acetate 95:5 (v/v, eluent); H NMR (400 MHz,
CDCl3) δ 0.90 (t, J = 7.4 Hz, 3H), 1.08−2.12 (m, 27H), 4.09 (t, J =
6.6 Hz, 2H), 6.22 (d, J = 15.4 Hz, 1H), 7.04 (ddd, J = 1.7, 11.5, 15.4
Hz, 3H), 7.06−7.11 (m, 2H), 7.67 (dd, J = 11.5, 19.3 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.7, 19.1, 25.8 (br), 26.1 (d, J = 2.3 Hz),
26.3 (d, J = 3.1 Hz), 26.48 (d, J = 13.5 Hz), 26.52 (d, J = 13.3 Hz),
30.6, 37.3 (d, J = 49.7 Hz), 64.5, 127.3, 128.6 (d, J = 1.2 Hz), 129.0,
129.2 (d, J = 3.6 Hz), 136.0 (d, J = 7.4 Hz), 138.4 (d, J = 15.8 Hz),
140.7 (d, J = 55.6 Hz), 144.4 (d, J = 11.2 Hz), 166.5; 31P{1H} NMR
(162 MHz, CDCl3) δ 63.5; HRMS m/z calcd for C27H40O2PS (M +
H+) 459.2481, found 459.2508.
(E)-Dicyclohexyl(2-(1-phenylprop-1-en-2-yl)phenyl)-
phosphine Sulfide (7a). Mp 160−161 °C (white solid), 49 mg
1
(47%); hexane/ethyl acetate 95:5 (v/v, eluent); H NMR (400 MHz,
CDCl3) δ 1.09−2.00 (m, 20H), 2.29 (d, J = 1.4 Hz, 3H), 2.34−2.48
(m, 2H), 6.32 (s, 1H), 7.20−7.25 (m, 1H), 7.30−7.54 (m, 7H), 8.53
(ddd, J = 1.4, 7.7, 14.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 22.0,
25.5 (br), 26.3 (d, J = 12.9 Hz), 26.5 (d, J = 13.4 Hz), 26.7 (br), 28.1
(br), 40.0 (d, J = 48.6 Hz), 126.90 (d, J = 11.4 Hz), 126.93 (d, J = 63.6
Hz), 127.2, 128.6, 128.7, 129.7 (d, J = 9.3 Hz), 130.1, 130.9 (d, J = 2.7
Hz), 136.5 (d, J = 10.8 Hz), 136.9, 138.5 (d, J = 1.4 Hz), 147.3 (d, J =
7.4 Hz); 31P{1H} NMR (162 MHz, CDCl3) δ 68.1; HRMS m/z calcd
for C27H36PS (M + H+) 423.2270, found 423.2287.
(E)-Dicyclohexyl(2-(1-phenylhex-1-en-2-yl)phenyl)phos-
phine Sulfide (7f). (E:Z = 97:3) Colorless oil, 34 mg (29%); hexane/
1
ethyl acetate 95:5 (v/v, eluent); H NMR (400 MHz, CDCl3) δ 0.82
(t, J = 7.2 Hz, 3H), 1.05−1.35 (m, 10H), 1.36−1.53 (m, 4H), 1.58−
1.89 (m, 8H), 1.91−2.04 (m, 2H), 2.10−2.70 (m, 3H), 2.70−3.32 (br,
1H), 6.33 (s, 1H), 6.46 (s, 1H, Z), 7.15−7.22 (m, 1H), 7.28−7.34 (m,
1H), 7.37−7.49 (m, 6H), 8.45 (ddd, J = 1.9, 7.3, 14.6 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.8, 23.0, 25.6 (d, J = 1.2 Hz), 26.3 (d, J
= 13.9 Hz), 26.5 (d, J = 13.6 Hz), 26.7 (d, J = 1.9 Hz), 27.8(br), 30.8,
34.1, 39.4 (d, J = 48.7 Hz), 126.8 (d, J = 11.3 Hz), 126.9 (d, J = 63.5
Hz), 127.0, 128.57, 128.60, 130.1, 130.5 (d, J = 2.6 Hz), 131.1 (d, J =
(E)-Dicyclohexyl(2-(1,2-diphenylvinyl)phenyl)phosphine
Sulfide (7b). Mp 196−197 °C (gray solid), 45 mg (37%); hexane/
1
ethyl acetate 90:10 (v/v, eluent); H NMR (400 MHz, CDCl3) δ
0.22−1.53 (m, 15H), 1.57−2.13 (m, 7H), 6.63 (s, 1H), 7.14−7.26 (m,
8H), 7.26−7.33 (m, 2H), 7.36−7.42 (m, 1H), 7.47−7.56 (m, 2H),
7654
dx.doi.org/10.1021/jo501542b | J. Org. Chem. 2014, 79, 7649−7655

The Journal of Organic Chemistry
Article
9.5 Hz), 136.0 (d, J = 11.0 Hz), 137.1, 143.8 (d, J = 1.8 Hz), 146.5 (d,
J = 7.6 Hz); 31P{1H} NMR (162 MHz, CDCl3) δ 67.3 (E), 69.6 (Z);
HRMS m/z calcd for C30H42PS (M + H+) 465.2739, found 465.2754.
(E)-(2-(6-Chloro-1-phenylhex-1-en-2-yl)phenyl)dicyclohexyl-
phosphine Sulfide (7g). (E:Z = 93:7) Pale yellow oil, 28 mg (23%);
hexane/ethyl acetate 90:10 (v/v, eluent); 1H NMR (400 MHz,
CDCl3) δ 1.07−1.36 (m, 9H), 1.38−1.50 (m, 2H), 1.50−1.55 (m,
1H), 1.59−1.76 (m, 8H), 1.79−1.87 (m, 2H), 1.92−2.07 (m, 2H),
2.18−2.61 (m, 3H), 2.75−3.19 (m, 1H), 3.34−3.48 (m, 2H), 6.36 (s,
1H), 6.44 (s, 1H, Z), 7.17−7.23 (m, 1H), 7.27−7.33 (m, 1H), 7.38−
7.51 (m, 6H), 8.28 (ddd, J = 1.4, 7.6, 13.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 25.6 (br), 25.7, 26.4 (d, J = 13.4 Hz), 26.5 (d, J = 13.4
Hz), 26.6 (br), 27.5 (br), 32.6, 33.7, 39.6 (d, J = 48.4 Hz), 44.5, 126.8
(d, J = 11.3 Hz), 126.9 (d, J = 63.7 Hz), 127.0, 128.57, 128.59, 130.4,
130.5 (d, J = 2.7 Hz), 131.4 (d, J = 9.3 Hz), 135.1 (d, J = 10.4 Hz),
137.1, 143.1 (d, J = 2.2 Hz), 147.0 (d, J = 7.3 Hz); 31P{1H} NMR (162
MHz, CDCl3) δ 60.7 (Z), 65.3 (E); HRMS m/z calcd for C30H41ClPS
(M + H+) 499.2350, found 499.2360.
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ASSOCIATED CONTENT
■
S
* Supporting Information
1
Copies of H and 13C NMR spectra of products. This material
is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: satoh@chem.eng.osaka-u.ac.jp.
*E-mail: miura@chem.eng.osaka-u.ac.jp.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by Grants-in-Aid from MEXT, JSPS,
and JST, Japan.
■
(6) For example, see: (a) Jarvis, A.; Whitwood, A. C.; Fairlamb, I. J. S.
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