Platinum-catalyzed highly selective thiocarbonylation of acetylenes with thiols and carbon monoxide

Article abstract of DOI:10.1016/S0040-4020(03)00485-X

A novel carbonylative addition of thiols (RSH) to terminal acetylenes (R′-C≡CH) takes place successfully in the presence of platinum catalysts under the pressure of carbon monoxide, providing α,β-unsaturated thioesters (R′-C(C(O)SR)=CH₂) in good yields regioselectively. This 'hydrothiocarbonylation' reaction of acetylenes may include the formation of the platinum sulfide complex as key species.

Full text of DOI:10.1016/S0040-4020(03)00485-X

Tetrahedron 59 (2003) 3521–3526
Platinum-catalyzed highly selective thiocarbonylation of
acetylenes with thiols and carbon monoxide
Jun-ichi Kawakami,a Masanori Mihara,b Ikuyo Kamiya,c Mitsuhiro Takeba,b Akiya Ogawac
and Noboru Sonodad
,
*
aChemical Development Laboratories, Takeda Chemical Industries, Ltd., 2-17-85 Jusohonmachi, Yodogawa-ku, Osaka 532-8686, Japan
bDepartment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
cDepartment of Chemistry, Faculty of Science, Nara Women’s University, Kitauoyanishi-machi, Nara 630-8506, Japan
dDepartment of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-0073, Japan
Received 8 January 2003; accepted 19 March 2003
Abstract—A novel carbonylative addition of thiols (RSH) to terminal acetylenes (R0 –CuCH) takes 0place successfully in the presence of
platinum catalysts under the pressure of carbon monoxide, providing a,b-unsaturated thioesters (R –C(C(O)SR)vCH2) in good yields
regioselectively. This ‘hydrothiocarbonylation’ reaction of acetylenes may include the formation of the platinum sulfide complex as key
species. q 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
selectively into the terminal and inner positions of
acetylenes, respectively. Furthermore, we have disclosed
that switching the catalyst simply from RhH(CO)(PPh3)3 to
Pt(PPh3)4 leads to a sharp reversal of regioselectivity of CO
introduction (‘hydrothiocarbonylation’) (Eq. (1)).20
Although the transition-metal-catalyzed reactions of
organic silicon,1 tin,2 and boron3 compounds have been
established for effecting a wide range of synthetic reactions,
the use of organosulfur compounds in transition-metal-
catalyzed reactions has been largely unexplored.4 Most
probably, the widespread prejudice that ‘sulfur compounds
are catalyst poisons’ has precluded investigation in this area.
Very recently, however, transition-metal-catalyzed highly
selective methods for the introduction of sulfur-containing
groups into carbon–carbon unsaturated bonds have been
reported,5 i.e. bisthiolation,6–8 hydrothiolation,9 thiobora-
tion,10 thiosilylation,11 thiophosphorylation,12 thioesterifi-
cation,13 S-propargylation or allylation of thiols,14 and
carbothiolation,15 etc.16 With regard to the transition-metal-
catalyzed reaction of thiols with carbon monoxide, the
Co2(CO)8-catalyzed desulfurizative carbonylation of thiols
was reported as a series of pioneering work.17 The
Co2(CO)8-catalyzed carbonylation of organic diselenide or
ditelluride has also been developed to give the correspond-
ing seleno and telluro ethers, respectively.18
ð1Þ
In this paper, we describe full details of this platinum-
catalyzed carbonylative addition of thiols to acetylenes
under the pressure of carbon monoxide. This platinum-
catalyzed reaction provides a general method for the
regioselective synthesis of a,b-unsaturated thioesters.
2. Results and discussion
Recently, we have discovered the first example of
RhH(CO)(PPh3)3-catalyzed ‘thioformylation’ of acetylenes
with thiols and carbon monoxide (Eq. (1)).19 This
thioformylation exhibits the excellent regioselectivity
where carbon monoxide and a thio group are introduced
2.1. Screening of Group 10 transition-metal-catalyzed
reaction of 1-octyne with benzenethiol and carbon
monoxide
Our recent investigations have proved that transition metal
complexes such as Pd, Pt and Rh complexes are effective
catalysts for regioselective hydrothiolation of carbon–
carbon unsaturated compounds with thiols.9a,c,d Therefore,
Keywords: thiocarbonylation; platinum; thiols; carbon monoxide;
acetylenes.
*
Corresponding author; e-mail: a.ogawa@cc.nara-wu.ac.jp
0040–4020/03/$ - see front matter q 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0040-4020(03)00485-X

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J. Kawakami et al. / Tetrahedron 59 (2003) 3521–3526
it might be expected that these complexes exhibit catalytic
activities toward the desired carbonylative addition of thiols
to acetylenes in the presence of carbon monoxide. At first,
we started the carbonylative addition by using Pd(OAc)2,
which is a useful catalyst for the addition of thiols to
acetylenes. However, the attempted reaction provided only
small amounts of the carbonylative addition product 5a21
and the thiol addition product 6a with the recovery of 80%
of the starting thiol (Eq. (2), condition a). This result clearly
indicates the pressurized carbon monoxide retarded the
catalytic activity of Pd(OAc)2 even for the simple addition
reaction.
and the carbonylative addition of diaryl disulfides to
terminal acetylenes under the pressure of carbon mon-
oxide.6 However, the attempted reaction of benzenethiol
with 1-octyne and carbon monoxide in the presence of
Pd(PPh3)4 provided carbonylation products 4a and 5a in 4
and 13% yields, respectively (entry 2). Palladium com-
plexes such as PdCl2(PPh3)2, PdCl2(PhCN)2 and Pd2(dba)3
resulted in the formation of a complex mixture (entries
3–5). As the result, palladium complexes examined did not
exhibit high catalytic activity for the desired carbonylative
addition.22 Interestingly, platinum complex like Pt(PPh3)4
exhibited relatively high catalytic activity toward the
desired carbonylation giving 4a in 32% yield (entry 6).
The reaction in the presence of NiCl2(PPh3)2 or in the
absence of catalyst did not afford the carbonylation products
(entries 7 and 8).
2.2. Pt(PPh3)4-Catalyzed hydrothiocarbonylation of
acetylenes with thiols and carbon monoxide
ð2Þ
As mentioned above (entry 6 in Table 1), the Pt(PPh3)4-
catalyzed reaction of 1-octyne (1a) with benzenethiol (2a)
and carbon monoxide provided 4a in 32% yield. We
optimized this Pt(PPh3)4-catalyzed reaction by examining
the reactions conducted under various reaction conditions
(Eq. (4), Table 2).
A similar reaction in acetonitrile led to the increase in the
yield of the product 5a slightly (Eq. (2), condition b). Next
we examined the reaction of benzenethiol with 1-octyne and
carbon monoxide under similar conditions by employing
some other Group 10 transition metal catalysts, and the
results are shown in Table 1 (Eq. (3)).
ð4Þ
When the reaction of 1-octyne (1.5 equiv.) was carried out
under 3 MPa of carbon monoxide at 1208C for 15 h, the
yield of the a,b-unsaturated thioester (4a) was increased to
60% (entry 1). The hydrothiocarbonylation product (4a),
which has an a,b-unsaturated carbonyl unit, is subjected to
conjugate addition of benzenethiol to give 8a in 14% yield
concomitantly (entry 1). However, the use of excess
1-octyne (5.5 equiv.) in this reaction afforded 4a in 83%
yield exclusively (entry 3). On the other hand, the reaction
employing excess benzenethiol (2 equiv.) provided 8a
predominantly (entry 4).
ð3Þ
Pd(PPh3)4 is an excellent catalyst for both the stereo-
selective addition of diaryl disulfides to terminal acetylenes
ð5Þ
Table 1. Group 10 transition-metal-catalyzed reaction of 1-octyne with
benzenethiol and carbon monoxide
Entry
Catalyst
Yield (%)a
Table 2. Pt(PPh3)4-Catalyzed reaction of 1-octyne with benzenethiol and
carbon monoxide
3a
4a
5a
6a
7aþ7a0
Entry
Molar ratio of 1a/2a
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(PPh3)4
PdCl2(PPh3)2
PdCl2(PhCN)2
Pd2(dba)3
Pt(PPh3)4
NiCl2(PPh3)2
None
0
0
0
0
0
0
0
0
0
4
13
0
7
13
19
7
5
7
2
6
0
1
20
0
0
8
0
0
0
0
4a
8a
0
Trace
Trace
0
1
2
3
4
1.5
3.5
5.5
0.5
15
15
1
60
71
83
–
14
6
–
77
32
Trace
0
Trace
0
0
15
Reaction condition. 1a (1 mmol), 2a (1 mmol), CO (3 MPa), catalyst
(2 mol%), CH3CN (1 mL), 1008C, 15 h.
Reaction condition. 1a (2.5–27.5 mmol), 2a (5 mmol), CO (3 MPa),
Pt(PPh3)4 (3 mol%), CH3CN (5 mL), 1208C.
Based on 2a employed.
a
a
Determined by 1H NMR.

J. Kawakami et al. / Tetrahedron 59 (2003) 3521–3526
3523
Table 4. Pt(PPh3)4-Catalyzed hydrothiocarbonylation of acetylenes with
cyclohexanethiol and carbon monoxide
Entry
Alkyne 1, R
Molar ratio of 1/2b Product 40 Isolated yield
(%)a
nC6H13
7.5
1.0
0.5
4d
4d
4d
4h
4i
94
99
99b
87
82
62
ð6Þ
1
2
3
4
5
6
Table 3 lists the results of the Pt(PPh3)4-catalyzed
hydrothiocarbonylation using some thiols and acetylenes
(Eq. (5)). The hydrothiocarbonylation with aromatic thiols
such as p-methoxybenzenethiol took place regioselectively
to provide the a,b-unsaturated thioesters in good yields
(entry 2). In the case of aliphatic thiols, the same
hydrothiocarbonylation also proceeded smoothly with
excellent regioselectivity (entries 3 and 4). Similar con-
ditions can be employed with aliphatic acetylenes (entries
5–7). Noteworthy is that Pt(PPh3)4 exhibits an excellent
catalytic activity for the regioselective hydrothiocarbonyl-
ation with aliphatic thiols, being different from the
Rh-catalyzed thioformylation, which takes place only in
the case using aromatic thiols.19 When the carbonylation of
5-hydroxy-1-pentyne was carried out in the presence of
benzenethiol (1 equiv.) and Pt(PPh3)4 (3 mol%) under
3 MPa of carbon monoxide at 1208C for 4 h, the
cyclocarbonylation of 5-hydroxy-1-pentyne took place
successfully to give a-[(phenylthio)methyl]-d-lactone (9)
selectively in 73% yield (Eq. (6)).23
(CH3)2CH(CH2)2 1.0
NC(CH2)3
Ph
1.0
1.0
4j
Reaction condition. 1 (5–37.5 mmol), 2b (5–10 mmol), CO (3 MPa),
Pt(PPh3)4 (3 mol%), CH3CN (5 mL), 1208C, 1–7 h.
Based on cyclohexanethiol employed.
a
b
Based on acetylene employed.
aromatic acetylenes also took place regioselectively (entry
6).
ð8Þ
As mentioned above, hydrothiocarbonylation product 4d
can be obtained in high yield, when the Pt(PPh3)4-catalyzed
reaction was carried out using 1-octyne (1 equiv.) under
3 MPa of carbon monoxide at 1208C (Eq. (8), Table 5,
entry 1). Lower temperature (808C) only gave 4d in 24%
yield and recovered cyclohexylthiol (entry 2). Under
0.5 MPa of carbon monoxide, the carbonylation proceeds
smoothly (entry 3).
ð7Þ
We next investigated the Pt(PPh3)4-catalyzed hydrothio-
carbonylation of aliphatic thiol such as cyclohexanethiol
(2b) in further details (Eq. (7), Table 4). In the case of
benzenethiol, the use of excess acetylenes is essential to
depress the further addition reaction of benzenethiol to the
a,b-unsaturated thioesters, while the hydrothiocarbonyl-
ation with aliphatic thiols, which are less acidic than
aromatic ones, proceeds smoothly by the use of equimolar
amount of acetylene to give the a,b-unsaturated thioesters
regioselectively in excellent yield (entry 2). Even in the case
using excess amounts of thiols, the a,b-unsaturated
thioester (4d) was obtained selectively in good yield
(entry 3).
2.3. A possible reaction pathway for Pt(PPh3)4-catalyzed
hydrothiocarbonylation of acetylenes with thiols and
carbon monoxide
To explore the reaction pathway for the Pt(PPh3)4-catalyzed
hydrothiocarbonylation, stoichiometric reaction of the
platinum catalyst with benzenethiol was examined. The
equimolar reaction of Pt(PPh3)4 with PhSH at 208C in
acetonitrile under argon atmosphere afforded a yellow solid
10a (Eq. (9)). 1H NMR spectra indicated the appearance of
the signal at d 210.01. This result and the melting point of
the yellow solid suggest the formation of trans-
PtH(SPh)(PPh3)2 (10a) reported in the literature.24 The
reaction of benzenethiol with 1-octyne (1a) in the presence
of complex 10a as a catalyst afforded the corresponding
product 4a in good yield (Eq. (10)).
Entries 4–6 in Table 4 show the results of the Pt(PPh3)4-
catalyzed hydrothiocarbonylation of cyclohexylthiol with
several terminal acetylenes. The hydrothiocarbonylation of
ð9Þ
Table 3. Pt(PPh3)4-Catalyzed hydrothiocarbonylation of acetylenes with
thiols and carbon monoxide
Entry
Alkyne 1, R1
nC6H13
Thiol 2, R2 Product 4 Isolated yield (%)a
Table 5. Pt(PPh3)4-Catalyzed hydrothiocarbonylation of 1-octyne with
cyclohexanethiol and carbon monoxide
1
2
3
4
5
6
7
Ph 4a
p-MeO–C6H4 4b
83
86
87
94
70
63
75
Entry
CO (MPa)
Temperature (8C)
Product 4d, Yield (%)a
nC8H17
cC6H11
4c
4d
4e
4f
(CH3)2CH(CH2)2 Ph
PhCH2
NC(CH2)3
1
2
3
3
3
0.5
120
80
120
99
24
85
4g
Reaction condition. 1 (37.5 mmol), 2a (5 mmol), CO (3 MPa), Pt(PPh3)4
(3 mol%), CH3CN (5 mL), 1208C, 1–7 h.
Based on thiols employed.
Reaction condition. 1 (5 mmol), 2b (5 mmol), CO (0.5–3 MPa), Pt(PPh3)4
(3 mol%), CH3CN (5 mL), 80–1208C, 2 h.
Based on cyclohexanethiol employed.
a
a

3524
J. Kawakami et al. / Tetrahedron 59 (2003) 3521–3526
(silica gel, 25–40 mm, length 310 mm, i.d. 25 mm, eluent
n-hexane–Et2O¼4:1).
4.1.1. 2-(Phenylthiocarbonyl)-1-octene (4a). A colorless
1
oil; H NMR (270 MHz, CDCl3) d 0.88 (t, J¼6.8 Hz, 3H),
1.20–1.40 (m, 6H), 1.48 (quint, J¼6.8 Hz, 2H), 2.34 (t,
J¼7.3 Hz, 2H), 5.65 (s, 1H), 6.21 (s, 1H), 7.35–7.50 (m,
5H); 13C NMR (68 MHz, CDCl3) d 14.0, 22.5, 28.2, 28.8,
31.5, 32.0, 122.7, 127.8, 129.1, 129.3, 134.9, 148.4, 191.7;
IR (NaCl) 3070, 2927, 2856, 1680, 1478, 1440, 965, 745,
688 cm21; MS (EI), m/z¼248 (Mþ, 13.6). Anal. calcd for
C15H20OS: C, 72.53; H, 8.12; S, 12.91. Found: C, 72.34; H,
8.17; S, 12.82.
4.1.2. 2-(p-Methoxyphenylthiocarbonyl)-1-octene (4b). A
colorless oil; 1H NMR (270 MHz, CDCl3) d 0.88 (t,
J¼6.8 Hz, 3H), 1.20–1.40 (br s, 6H), 1.48 (quint,
J¼6.8 Hz, 2H), 2.34 (t, J¼7.6 Hz, 2H), 3.82 (s, 3H), 5.64
(s, 1H), 6.20 (s, 1H), 6.94 (d, J¼8.8 Hz, 2H), 7.33 (d,
J¼8.8 Hz, 2H); 13C NMR (68 MHz, CDCl3) d 14.0, 22.5,
28.2, 28.9, 31.5, 32.0, 55.3, 114.8, 18.5, 122.5, 136.4, 148.4,
160.6, 192.7; IR (NaCl) 3090, 2928, 2857, 1678, 1626,
Scheme 1.
ð10Þ
1594, 1495, 1463, 1291, 1250, 1174, 1033, 966, 826 cm21
;
MS (EI), m/z¼278 (Mþ, 43.5). Anal. calcd for C16H22OS:
C, 69.02; H, 7.97. Found: C, 69.26; H, 8.08.
Although elucidation of the precise mechanism requires
further detailed investigation, the catalytic cycle A for
hydrothiocarbonylation is proposed as
4.1.3. 2-(Phenylthiocarbonyl)-5-methyl-1-hexene (4e). A
1
pale yellow oil; H NMR (300 MHz, CDCl3) d 0.90 (d,
a possible
reaction path (Scheme 1).25 The oxidative addition of
R0SH to PtLn affords PtH(SR0)Ln (10). The insertion of CO
into the Pt–S bond of 10 leads to 11. The insertion of
acetylene into Pt–C bond of 11 forms the vinylplatinum
complex (12), and the subsequent reductive elimination
with the regeneration of PtLn provides the hydrothio-
carbonylation product 4.
J¼6.6 Hz, 6H), 1.37 (q, J¼7.6 Hz, 2H), 1.58 (m, 1H), 2.35
(t, J¼7.8 Hz, 2H), 5.68 (t, J¼7.8 Hz, 2H), 5.68 (s, 1H), 6.22
(s, 1H), 7.40–7.43 (m, 5H); 13C NMR (75 MHz, CDCl3) d
22.1, 27.4, 29.6, 37.0, 122.6, 127.6, 129.0, 129.2, 134.8,
148.5, 191.8; IR (NaCl) 2928, 2868, 1681, 1626, 1468,
1439, 910, 745, 689 cm21; MS (EI), m/z¼234 (Mþ, 17.2);
HRMS calcd for C14H18OS 234.1078, found 234.1080.
4.1.4. 2-(Phenylthiocarbonyl)allylbenzene (4f). A brown
oil; 1H NMR (270 MHz, CDCl3) d 3.67 (s, 2H), 5.57 (s, 1H),
6.33 (s, 1H), 7.18–7.40 (m, 10H); 13C NMR (68 MHz,
CDCl3) d 37.8, 124.6, 126.5, 127.5, 128.5, 129.1, 129.3,
134.9, 138.0, 147.6, 191.2; IR (NaCl) 3061, 3027, 1676,
1626, 1495, 1478, 1440, 973, 747, 705 cm21; MS (EI),
m/z¼256 (Mþ, 7.1). Anal. calcd for C16H14OS: C, 75.56; H,
5.55. Found: C, 75.76; H, 5.63.
3. Conclusion
We have developed the platinum-catalyzed highly selective
hydrothiocarbonylation of acetylenes with thiols and carbon
monoxide. a,b-Unsaturated thioesters can be produced in
good yields in the presence of catalytic amounts of
Pt(PPh3)4. This reaction provides a general method for the
regioselective introduction of thiols and carbon monoxide to
acetylenes.
4.1.5. 2-(Phenylthiocarbonyl)-5-cyano-1-pentene (4g). A
pale yellow oil; 1H NMR (270 MHz, CDCl3) d 1.87 (quint,
J¼7.3 Hz, 2H), 2.35 (t, J¼7.1 Hz, 2H), 2.51 (t, J¼7.6 Hz,
2H), 5.81 (s, 1H), 6.34 (s, 1H), 7.42 (s, 5H); 13C NMR
(68 MHz, CDCl3) d 16.5, 24.0, 31.1, 119.1, 124.9, 127.1,
129.2, 129.5, 134.9, 145.8, 191.3; IR (NaCl) 3061, 2939,
2246, 1674, 1628, 1478, 1440, 970, 748, 690 cm21; MS
(EI), m/z¼231 (Mþ, 5.2). Anal. calcd for C13H13NOS: C,
67.50; H, 5.66; N, 6.06; S, 13.86. Found: C, 67.27; H, 5.73;
N, 6.05; S, 13.49.
4. Experimental
4.1. General procedure for the Pt(PPh3)4-catalyzed
hydrothiocarbonylation of acetylenes with carbon
monoxide and aromatic thiols
In a 50 mL stainless steel autoclave with a magnetic stirring
bar under argon atmosphere were placed Pt(PPh3)4
(3 mol%), acetonitrile (5 mL), acetylene (37.5 mmol), and
aromatic thiol (5 mmol). Carbon monoxide was purged for
three times and then charged at 3 MPa. The reaction was
conducted with magnetic stirring for 2 h upon heating at
1208C. After carbon monoxide was purged, the resulting
mixture was filtered through Celite and concentrated in
vacuo. Purification of the product was carried out by MPLC
4.2. General procedure for the Pt(PPh3)4-catalyzed
hydrothiocarbonylation of acetylenes with carbon
monoxide and aliphatic thiols
In a 50 mL stainless steel autoclave with a magnetic stirring
bar under argon atmosphere were placed Pt(PPh3)4
(3 mol%), acetonitrile (5 mL), acetylene (5 mmol), and

J. Kawakami et al. / Tetrahedron 59 (2003) 3521–3526
3525
aliphatic thiol (5 mmol). Carbon monoxide was purged for
Acknowledgements
three times and then charged at 3 MPa. The reaction was
conducted with magnetic stirring for 2 h upon heating at
1208C. After carbon monoxide was purged, the resulting
mixture was filtered through Celite and concentrated in
vacuo. Purification of the product was carried out by MPLC
(silica gel, 25–40 mm, length 310 mm, i.d. 25 mm, eluent
n-hexane–Et2O¼4:1).
This research was supported in part by a Grant-in-Aid for
Scientific Research on Priority Areas (A) ‘Exploitation of
Multi-Element Cyclic Molecules’ from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
4.2.1. 2-(n-Octylthiocarbonyl)-1-octene (4c). A colorless
1
References
liquid; H NMR (270 MHz, CDCl3) d 0.88 (t, J¼6.8 Hz,
6H), 1.20–1.50 (m, 18H), 1.59 (quint, J¼7.3 Hz, 2H), 2.33
(t, J¼7.6 Hz, 2H), 5.51 (s, 1H), 6.05 (s, 1H); 13C NMR
(68 MHz, CDCl3) d 14.0, 22.5, 22.6, 28.2, 28.85, 28.88,
29.08, 29.13, 29.5, 31.6, 31.8, 121.4, 148.8, 194.0; IR
(NaCl) 2927, 2856, 1666, 1627, 1458, 974, 928 cm21; MS
(EI), m/z¼284 (Mþ, 5.3). Anal. calcd for C17H32OS: C,
71.77; H, 11.34. Found: C, 71.63; H, 11.32.
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4.2.2. 2-(c-Hexylthiocarbonyl)-1-octene (4d). A colorless
1
liquid; H NMR (270 MHz, CDCl3) d 0.88 (t, J¼6.8 Hz,
3H), 1.20–1.36 (m, 6H), 1.37–1.54 (m, 6H), 1.62 (m, 2H),
1.72 (br quint, 2H), 1.94 (br quint, 2H), 2.31 (t, J¼7.6 Hz,
2H), 3.53 (m, 1H), 5.49 (s, 1H), 6.03 (s, 1H); 13C NMR
(68 MHz, CDCl3) d 14.0, 22.5, 25.6, 26.0, 28.2, 28.9, 31.6,
31.8, 33.1, 42.3, 121.3, 149.0, 193.7; IR (NaCl) 2929, 2854,
2360, 1662, 1626, 1449, 1378, 1342, 1264, 1208, 1103, 996,
973, 928, 888, 818, 725, 654 cm21; MS (EI), m/z¼254 (Mþ,
18.5); HRMS calcd for C15H26OS 254.1704, found
254.1705.
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4.2.3. 2-(c-Hexylthiocarbonyl)-5-methyl-1-hexene (4h).
1
A colorless liquid; H NMR (270 MHz, CDCl3) d 0.90 (t,
J¼6.8 Hz, 6H), 1.29–1.72 (m, 11H), 1.94 (m, 2H), 2.32 (t,
J¼8.1 Hz, 2H), 3.53 (m, 1H), 5.50 (s, 1H), 6.03 (s, 1H); 13C
NMR (68 MHz, CDCl3) d 22.4, 25.6, 26.0, 27.8, 29.7, 33.1,
37.4, 42.3, 121.3, 149.2, 193.8; IR (NaCl) 2931, 2854, 1661,
1627, 1468, 1449, 1385, 1367, 1342, 1265, 1225, 1204,
1106, 984, 919, 888, 818, 653 cm21; MS (EI), m/z¼240
(Mþ, 3.0). Anal. calcd for C14H24OS: C, 69.95; H, 10.06.
Found: C, 70.02; H, 10.18.
3. (a) Miyaura, N. In Catalytic Heterofunctionalization; Togni,
A., Gru¨tzmacher, H., Eds.; Wiley-VCH: Weinheim, 2001;
pp 1–45. (b) Miyaura, N. Top. Curr. Chem. 2002, 219, 11.
(c) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957.
(d) Suzuki, A.; Miyaura, N. J. Synth. Org. Chem. Jpn 1993, 51,
1043. (e) Burgess, K.; Ohlmeyer, M. J. Chem. Rev. 1991, 91,
1179.
4.2.4. 2-(c-Hexylthiocarbonyl)-5-cyano-1-pentene (4i). A
1
pale yellow oil; H NMR (270 MHz, CDCl3) d 1.30–1.72
4. (a) Roberto, A. S.-D. Organometallic Modeling of the
Hydrosulfurization and Hydrodenitrogenation Reaction;
Kluwer Academic: Dordrecht, 2002. (b) Weber, T.; Prins,
R.; van Santen, A. Transition Metal Sulphides Chemistry and
Catalysis; Kluwer Academic: Dordrecht, 1997. (c) Stiefel,
E. I.; Matsumoto, K. Transition Metal Sulfur Chemistry
Biological and Industrial Significance; American Chemical
Society: Washington, DC, 1996.
(m, 8H), 1.85 (quint, J¼7.3 Hz, 2H), 1.94 (m, 2H), 2.35 (t,
J¼7.1 Hz, 2H), 2.48 (t, J¼7.3 Hz, 2H), 3.54 (m, 1H), 5.63
(s, 1H), 6.15 (s, 1H); 13C NMR (68 MHz, CDCl3) d 16.5,
24.0, 25.5, 25.9, 30.8, 33.0, 42.5, 119.2, 123.5, 146.3, 193.1;
IR (NaCl) 2932, 2854, 2363, 2246, 1657, 1627, 1449, 1343,
1264, 1208, 1056, 997, 975, 933, 888, 871, 818, 757 cm21
;
MS (EI), m/z¼237 (Mþ, 2.1). Anal. calcd for C13H19NOS:
C, 65.78; H, 8.07; N, 5.90. Found: C, 66.14; H, 8.28; N,
5.94.
5. (a) Ogawa, A. Handbook of Organopalladium Chemistry for
Organic Synthesis; Negishi, E., Ed.; Wiley: New york, 2002;
p 2841 Chapter VII.6. (b) El Ali, B.; Alper, H. Handbook of
Organopalladium Chemistry for Organic Synthesis; Negishi,
E., Ed.; Wiley: New york, 2002; p 2333 Chapter VI.6.
(c) Kuniyasu, H.; Kurosawa, H. Chem. Eur. J. 2002, 8, 2660.
(d) Ogawa, A.; Hirao, T. Science of Synthesis; Lautens, M.,
Trost, B. M., Eds.; Georg Thieme: Stuttgart, 2001; Vol. 1,
p 389. (e) Takacs, J. M.; Vayalakkada, S.; Jiang, X. Science of
Synthesis; Lautens, M., Trost, B. M., Eds.; Georg Thieme:
Stuttgart, 2001; Vol. 1, p 265. (f) Takacs, J. M.; Jiang, X.;
Vayalakkada, S. Science of Synthesis; Lautens, M., Trost,
B. M., Eds.; Georg Thieme: Stuttgart, 2001; Vol. 1, p 63.
4.2.5. 2-(c-Hexylthiocarbonyl)styrene (4j). 1H NMR
(270 MHz, CDCl3) d 1.29–1.72 (m, 8H), 1.97 (quint like,
2H), 3.60 (m, 1H), 5.75 (s, 1H), 6.15 (s, 1H), 7.33–7.37 (m,
5H); 13C NMR (68 MHz, CDCl3) d 25.6, 26.0, 32.9, 42.9,
122.3, 128.2, 128.3, 128.5, 136.2, 148.6, 193.5; IR (NaCl)
2930, 2853, 1662, 1612, 1494, 1447, 1295, 1265, 1118,
1004, 995, 972, 935, 787, 774, 698, 666 cm21; MS (EI),
m/z¼246 (Mþ, 13.4); HRMS calcd for C15H18OS 246.1078,
found 246.1067.

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J. Kawakami et al. / Tetrahedron 59 (2003) 3521–3526
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