Transition-metal-catalyzed cyanochalcogenation of alkynes with chalcogenocyanates

Article abstract of DOI:10.1246/bcsj.20100187

Tetrakis(triphenylphosphine)palladium(0) catalyzes the highly regioselective addition of phenyl thiocyanate to terminal alkynes, which attains the simultaneous introduction of thio and cyano groups into the internal and terminal positions of alkynes, respectively. In addition, dicobalt octacarbonyl indicates moderate catalytic activity toward the same cyanothiolation of alkynes with excellent regioselectivity. By using [Co₂(CO)₈] as the catalyst, novel cyanoselenation of alkynes with phenyl selenocyanate has also been attained in moderate yield with excellent regioselectivity.

Full text of DOI:10.1246/bcsj.20100187

© 2011 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 84, No. 2, 155–163 (2011)
155
Selected Papers
Transition-Metal-Catalyzed Cyanochalcogenation
of Alkynes with Chalcogenocyanates
Toshiya Ozaki,1 Akihiro Nomoto,1 Ikuyo Kamiya,2 Jun-ichi Kawakami,2 and Akiya Ogawa*1
1Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531
2Department of Chemistry, Faculty of Science, Nara Women’s University, Kitauoyanishi-machi, Nara 630-8506
Received July 7, 2010; E-mail: ogawa@chem.osakafu-u.ac.jp
Tetrakis(triphenylphosphine)palladium(0) catalyzes the highly regioselective addition of phenyl thiocyanate to
terminal alkynes, which attains the simultaneous introduction of thio and cyano groups into the internal and terminal
positions of alkynes, respectively. In addition, dicobalt octacarbonyl indicates moderate catalytic activity toward the same
cyanothiolation of alkynes with excellent regioselectivity. By using [Co2(CO)8] as the catalyst, novel cyanoselenation of
alkynes with phenyl selenocyanate has also been attained in moderate yield with excellent regioselectivity.
The transition-metal-catalyzed reactions of organoboron,
organosilicon, and organotin compounds are utilized widely in
organic synthesis.1 In contrast, the transition-metal-catalyzed
reactions of group 16 compounds had been largely unexplored,
partly because these compounds were believed to be catalyst
poisons for a variety of transition-metal-catalyzed reactions.2
Recently, synthetically useful transition-metal-catalyzed reac-
Table 1. Catalytic Activity of Transition-Metal Complexes
on the Reaction of 1-Octyne with PhSCNa)
nC6H13
catalyst
nC6H13
1a
CN
+
PhSCN
solvent
PhS
2a
3a
Entry Catalyst
Solvent Temp/°C Time/h Yield/%b)
tions of organosulfur compounds have been developed.3
A
1
2
3
4
5
PdCl2
benzene 140
toluene 110
benzene 140
CH3CN 120
benzene 120
62
60
62
65
20
41
71
67
0
16
trace
0
0
0
series of transition-metal-catalyzed addition reactions of orga-
nosulfur and organoselenium compounds have been disclosed,
e.g., highly selective bisthiolation,4 hydrothiolation,5 and
thiocarbonylation5d,6 of unsaturated compounds such as alkynes
(and the corresponding reactions of selenium analogs7). These
reactions clearly demonstrate that the transition-metal catalysts
are indeed effective for the highly selective synthetic reactions
of organosulfur and organoselenium compounds based on the
cleavage of heteroatom-heteroatom and heteroatom-hydrogen
bonds. However, the introduction of sulfur groups to carbon-
carbon unsaturated compounds based on the sulfur-carbon
bond cleavage by the transition-metal catalysts is still rare.8
Herein we report highly regioselective cyanothiolation and
cyanoselenation of terminal alkynes with thio- and selenocya-
nates in the presence of transition-metal catalysts (eq 1).9-11
[Pd(PPh3)4]
[Pd2(dba)3]
NiCl2
[Pt(PPh3)4]
6c) CoCl2
CH3CN
CH2Cl2
140
140
140
7
8
[Co2(CO)8]
[RhH(CO)(PPh3)3] CH3CN
14
0
a) Reaction conditions: catalyst (10 mol %), 1a (1.0 mmol),
2a (1.0 mmol), solvent (1 mL). b) Determined by 1H NMR.
c) CoCl2 (5 mol %).
lysts indicated no catalytic activity (Entries 1, 3-6, and 8), low-
valent complexes of palladium and cobalt such as [Pd(PPh3)4]
and [Co2(CO)8] indicated catalytic activity toward the desired
cyanothiolation of 1-octyne (Entries 2 and 7). Although the
yields of the cyanothiolation product were low in these
[Pd(PPh3)4]- and [Co2(CO)8]-catalyzed reactions, excellent
regioselectivity was observed: thio and cyano groups were
introduced into the internal and terminal positions of 1-octyne,
regioselectivity.
To optimize the reaction conditions, a series of [Co2(CO)8]-
catalyzed reactions of 1-octyne (1a) with phenyl thiocyanate
was carried out under various conditions (Table 2). Interest-
ingly, the yield of the desired cyanothiolation product 3a was
improved when the reaction was carried out in the presence of
carbon monoxide: in the absence of carbon monoxide, the yield
of 3a was 14%, whereas the yield was improved up to 45% in
cat. Pd or Co
R
CN
ð1Þ
PhYCN
+
R
PhY
2 (Y = S)
3 (Y = S)
1
4 (Y = Se)
5 (Y = Se)
Results and Discussion
The reaction of phenyl thiocyanates with 1-octyne (1a) was
examined in the presence of several transition-metal catalysts
(Table 1). While PdCl2, [Pd2(dba)3] (dba: dibenzylideneace-
tone), NiCl2, [Pt(PPh3)4], CoCl2, and [RhH(CO)(PPh3)3] cata-
Published on the web January 28, 2011; doi:10.1246/bcsj.20100187

156
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
Cyanochalcogenation of Alkynes
nC6H13
PhSCN
+
+
CO
Table 2. [Co2(CO)8]-Catalyzed Addition of PhSCN to
1-Octyne in the Presence of COa)
1 equiv 3 MPa
nC6H13
1a
+
+
PhSCN
CO
complex A (10 mol%) nC6H13
CH2Cl2, r.t., 65 h
2a
CN
+
(PhS)2
49%
ð3Þ
nC6H13
PhS
3a, 35%
cat. [Co2(CO)8]
CH2Cl2
CN
+
(PhS)2
PhS
3a
Table 3. Influence of Solvents on the [Pd(PPh3)4]-Catalyzed
Cyanothiolationa)
6
Yield/%b) [E/Z]
Temp Time
nC6H13
+
PhSCN
Entry Additive
/°C
/h
3a
6
1c)
2d)
3e)
4
5
6
7
120
120
140
140
11
7 [0/100]
0
56
trace
55
1a
2a
84 34 [0/100]
71 14 [0/100]
60 45 [9/91]
72 31 [45/55]
68 16 [trace/100]
84 50 [78/22]
nC6H13
PhS
cat. [Pd(PPh3)4]
solvent
CN
(PhS)2 (30 mol %) 140
24
f)
PPh3 (20 mol %)
140
160
®
37
3a
Entry Solvent Temp/°C Time/h Yield/%b)
[E/Z]
a) Reaction conditions: [Co2(CO)8] (10 mol %), 1a (1.0 mmol),
2a (1.0 mmol), CH2Cl2 (1 mL), CO (3 MPa). b) Determined by
1H NMR. c) 1a (3 mmol). d) 2a (1.5 mmol). e) In the absence
of CO. f) Not determined.
1
2
3
4
5
6
7
8
benzene
toluene
xylene
120
120
120
120
120
80
66
66
66
66
66
24
24
66
61
44
34
42
12
9
[trace/µ100]
[trace/µ100]
[trace/µ100]
[trace/µ100]
[trace/µ100]
[trace/µ100]
[trace/µ100]
[12/88]
THF
CH3CN
benzene
benzene
benzene
the presence of 3 MPa of carbon monoxide (Entries 3 and 4).12
The addition of diphenyl disulfide or phosphine to the catalytic
system did not improve the yield of 3a (Entries 5 and 6). The
reaction of 1-octyne with 1 equivalent of phenyl thiocyanate
(2a) at higher temperature (160 °C) provided the desired
cyanothiolation product 3a in 50% yield along with 37% yield
of diphenyl disulfide (Entry 7). In this case, the E-isomer was
formed predominantly. Since the Z-isomer was obtained
predominantly at lower temperature (120-140 °C), the Z-isomer
might isomerize to E-isomer at higher temperature (160 °C).13
In this [Co2(CO)8]-catalyzed cyanothiolation, diphenyl disul-
fide was formed as a by-product abundantly.
120
140
12
56
a) Reaction conditions: [Pd(PPh3)4] (10 mol %), 1a (1.0 mmol),
2a (1.0 mmol), solvent (1 mL). b) Determined by H NMR.
1
Next, the [Pd(PPh3)4]-catalyzed cyanothiolation was inves-
tigated under various reaction conditions. To optimize the
reaction conditions at first, the [Pd(PPh3)4]-catalyzed reaction
of 1-octyne with phenyl thiocyanate was examined under
several reaction conditions (Table 3). The reaction was greatly
influenced by the solvent employed. Among the solvents
employed (benzene, toluene, xylene, THF, and CH3CN),
benzene was suitable for the present reaction to afford higher
yields of 3a, whereas the reaction in CH3CN resulted in the
low yield of 3a (Entries 1-5). When the cyanothiolation was
conducted at lower temperature (80 °C) or for shorter reaction
time (24 h), the reaction gave 3a in only 9% and 12% yields,
respectively (Entries 6 and 7). Prolonged reaction time led to a
great increase in yield (Entry 1). Higher temperature (140 °C)
led to the formation of 3a in 56% yield (Entry 8). Conse-
quently, upon heating at 120 °C in benzene, the desired
cyanothiolation product 3a was obtained in good yield with
excellent regioselectivity (Entry 1).
In the presence of several palladium catalysts, the cyano-
thiolation of 1-octyne with phenyl thiocyanate was examined,
and the results are summarized in Table 4. Pd(0) complex
as [Pd(PPh3)4] was the most effective catalyst toward this
cyanothiolation (Entry 1).14 When the [Pd(PPh3)4]-catalyzed
reaction in the presence of carbon monoxide was conducted,
the yield of the cyanothiolation product decreased (25%) and
thioester 3a¤, which is the carbonylative addition product
of diphenyl disulfide, was obtained in 18% yield (Entry 2).
The addition of phosphines such as triphenylphosphine and
diphenylphosphinopropane (DPPP) to palladium acetate re-
To get insight into the reaction pathway for the [Co2(CO)8]-
catalyzed cyanothiolation, the stoichiometric reaction of [Co2-
(CO)8] with PhSCN was examined (eq 2). The equimolar
reaction of [Co2(CO)8] with PhSCN at room temperature in
CH2Cl2 under an argon atmosphere afforded a black solid
(complex A). The IR spectra of complex A showed bridged
and terminal coordinated CO absorptions at 1854, 2036, and
¹1
2098 cm and CN absorption at 2137 cm¹1. From this result
and elemental analysis, it is assumed that complex A has a
cluster structure bridged by carbonyl, thio or cyano groups.
Furthermore, the catalytic reaction of 1-octyne with PhSCN in
the presence of complex A was examined and the reaction
afforded the cyanothiolation product 3a in 35% yield (eq 3).
ð2Þ
[Co2(CO)8] + PhSCN
1 equiv
complex A
CH2Cl2, r.t., 24 h
Anal. Calcd for [Co2(CO)2(CN)(SPh)]:
C, 34.97; H, 1.63; N, 4.53%.
Found: C, 35.03; H, 1.63; N, 4.53%.
mp: >300 °C IR: 1854, 2036, 2098 cm-1 (CO)
2137 cm-1 (CN)

T. Ozaki et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
157
sulted in the decrease in the yield of 3a (Entries 3 and 4). Pd(II)
complex such as PdCl2 exhibits no catalytic activity and the
starting materials were recovered unchanged (Entry 5).
By using the optimized reaction conditions (Table 4,
Entry 1), we next examined the [Pd(PPh3)4]-catalyzed cyano-
thiolation of some other terminal alkynes, and the results are
shown in Table 5. 5-Methyl-1-hexyne and 5-cyano-1-pentyne
underwent the regio- and stereoselective cyanothiolation,
affording the corresponding adducts in good yields (Entries 1
and 2). 1-Ethynylcyclohexene regioselectively provided the
conjugated cyanothiolation product as a stereoisomeric mixture
(Entry 4). The cyanothiolation of aromatic alkynes such as
phenylacetylene in benzene gave low yield (35%) of the
desired product; however, a similar reaction in the absence of
benzene led to the increase in the yield (84%, Entry 5).
Similarly, the reaction of 4-ethynyltoluene in the absence of
benzene afforded the cyanothiolation product in good yield
(81%, Entry 6). In contrast to PhSCN, the addition of aliphatic
thiocyanate such as n-butyl thiocyanate (n-BuSCN) resulted in
poor yield of the adduct (9% yield).
To get insight into the reaction pathway for this cyanothio-
lation, the equimolar reaction of [Pd(PPh3)4] with PhSCN in
benzene was conducted at room temperature to afford a yellow
solid (complex B) (eq 4). The IR spectrum of complex B
showed a CN absorption (2130 cm¹1). This and elemental
analysis suggest that the structure of complex B can be
assumed to be [Pd(CN)(PPh3)2(SPh)]. Furthermore, the X-ray
crystal structure analysis clearly indicates that complex B
is the mononuclear Pd(II) complex with trans-form, i.e.,
“trans-[Pd(CN)(PPh3)2(SPh)]” (for the X-ray analysis, see
Ref. 9).15,16
Table 4. Cyanothiolation of 1-Octyne Catalyzed by Palla-
dium Complexesa)
nC6H13
PhSCN
+
1a
2a
nC6H13
PhS
catalyst
benzene,120 °C
CN
3a
Time Yield
/h /%b)
Entry Catalyst
Additive
[E/Z]
ð4Þ
[Pd(PPh3)4] + PhSCN
benzene, r.t., 24 h
1 equiv
1
[Pd(PPh3)4]
66
66
61 [trace/µ100]
25 [trace/µ100]
47 [trace/µ100]
10 [trace/µ100]
0
2c) [Pd(PPh3)4] CO (3 MPa)
3
4
Pd(OAc)2 PPh3 (40 mol %) 73
Pd(OAc)2 DPPP (10 mol %) 66
[Pd(CN)(PPh3)2(SPh)]
Ph3P
PhS
CN
Pd
5d) PdCl2
62
PPh3
complex B
a) Reaction conditions: catalyst
(10 mol %), 1a (1.0 mmol), 2a (1.0
mmol), benzene (1 mL). b) Deter-
mined by 1H NMR. c) 1a (3.0
mmol) was employed, and thioester
3a¤ was obtained in 18% yield as a
by-product. d) 140 °C.
nC6H13
PhS
SPh
Anal. Calcd for C43H35NP2PdS:
O
C, 67.41; H, 4.60; N, 1.83%.
Found: C, 68.19; H, 4.66; N, 1.97%.
mp: 229-230 °C IR: 2130 cm-1 (CN)
3a′
Table 5. [Pd(PPh3)4]-Catalyzed Cyanothiolation of Terminal Alkynesa)
Entry
1
Alkyne
Product
Yield/%b)
[E/Z]c)
[1/99]
3b
60
1b
1c
1d
CN
PhS
PhS
3c
NC
CN
CN
2
3
48
53
[1/99]
NC
Ph
3d
[17/83]
Ph
PhS
3e
3f
4
5
1e
1f
56
84
[58/42]
[14/86]
CN
CN
PhS
Ph
Ph
PhS
CH3
6d)
81
[12/88]
CH3
1g
3g
CN
PhS
a) Reaction conditions: [Pd(PPh3)4] (10 mol %), alkyne (1.0 mmol), thiocyanate (1.0 mmol), benzene
(Entries 1 and 2), without benzene (Entries 3-6), 120 °C, 66 h. b) Isolated yield. c) Determined by
1H NMR. d) 20 h.

158
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
Cyanochalcogenation of Alkynes
nC6H13
PhSCN
+
the cleavage of sulfur-cyano bond; (ii) alkyne coordinates to
complex B; (iii) syn-thiopalladation (or syn-cyanopalladation)
of the alkyne forms (Z)-vinylpalladium intermediate; (iv)
reductive elimination of the cyanothiolation product occurs
with the retention of the stereochemistry along with regener-
ation of the catalyst.10c,10d,17
1 equiv
complex B (10 mol%)
nC6H13
ð5Þ
CN
benzene, 120 °C, 65 h
PhS
Next, the stoichiometric reaction of [Pd(PPh3)4] with aliphatic
thiocyanate such as n-butyl thiocyanate was examined. The
reaction of [Pd(PPh3)4] with 1 equivalent of n-BuSCN at room
temperature in benzene under an argon atmosphere afforded
a white solid (complex C) (eq 6). From the results of the
elemental analysis and IR spectrum of complex C, it is assumed
that complex C has the structure [Pd(CN)(PPh3)(SBu-n)].
58% [E/Z = 1/99]
A catalytic reaction of 1-octyne with PhSCN was examined
in the presence of complex B as the catalyst and the correspond-
ing cyanothiolation product was obtained in 58% yield (eq 5).
Scheme 1 shows a possible reaction pathway on the basis of
these results, which includes the following: (i) complex B is
formed via oxidative addition of PhSCN to [Pd(PPh3)4] with
ð6Þ
[Pd(PPh3)4] + n-BuSCN
benzene, r.t., 24 h
1 equiv
R
PdLn
CN
PhSCN
PhS
[Pd(CN)(PPh3)(SBu-n)]n
complex C
Anal. Calcd for C23H24NPPdS:
C, 57.09; H, 5.00; N, 2.89%.
R
PdLn CN
PhS PdLn CN
Found: C, 57.24; H, 5.00; N, 2.92%.
mp: 240 °C (dec.); IR: 2131 cm-1 (CN)
PhS
B
We succeeded in the X-ray analysis of complex C, clearly
indicating that complex C is a binuclear palladium(II) complex
bridged by thio groups (Figure 1). Each palladium atom
formed tetracoordinated complex and -SBu-n and -CN groups
of the complex were located in the cis-position.
It should be noted that the substituent on thiocyanate largely
affected the yield. In the case of an aromatic group on sulfur,
lone pairs of electrons on sulfur conjugate with ³-electrons of
R
R
PhS PdLn CN
Scheme 1. A possible pathway for the [Pd(PPh3)4]-catalyzed
cyanothiolation.
a)
b)
Figure 1. a) ORTEP drawing of complex C (50% probability thermal ellipsoids). All hydrogen atoms are omitted for clarity.
b) Phenyl rings are omitted for clarity. Selected bond lengths (¡) and angles (deg): Pd(1)-Pd(2) 3.0486(2), Pd(1)-S(1) 2.3478(5),
Pd(1)-S(2) 2.3489(6), Pd(1)-P(1) 2.2912(6), Pd(1)-C(9) 1.982(2), Pd(2)-S(1) 2.3544(6), Pd(2)-S(2) 2.3408(5), Pd(2)-P(2)
2.2983(5), Pd(2)-C(10) 1.983(2), Pd(2)-Pd(1)-S(1) 49.678(16), Pd(2)-Pd(1)-S(2) 49.338(14), Pd(2)-Pd(1)-P(1) 127.125(15),
Pd(2)-Pd(1)-C(9) 120.58(7), S(1)-Pd(1)-S(2) 80.48(2), S(1)-Pd(1)-P(1) 95.54(2), S(1)-Pd(1)-C(9) 170.00(6), S(2)-Pd(1)-P(1)
175.91(2), S(2)-Pd(1)-C(9) 94.08(7), P(1)-Pd(1)-C(9) 89.73(7), Pd(1)-Pd(2)-S(1) 49.489(13), Pd(1)-Pd(2)-S(2) 49.568(16),
Pd(1)-Pd(2)-P(2) 129.004(18), Pd(1)-Pd(2)-C(10) 122.79(6), S(1)-Pd(2)-S(2) 80.50(2), S(1)-Pd(2)-P(2) 96.85(2), S(1)-Pd(2)-
C(10) 172.27(6), S(2)-Pd(2)-P(2) 177.25(2), S(2)-Pd(2)-C(10) 94.11(7), P(2)-Pd(2)-C(10) 88.60(7).

T. Ozaki et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
159
Table 6. Transition-Metal-Catalyzed Reaction of 1-Octyne
with PhSeCNa)
nC6H13
+
PhSeCN
1a
4a
nC6H13
PhSe
catalyst
solvent
CN
5a
Temp Time Yield
Entry Catalyst
Solvent
/°C
/h
/%b)
1
2
3
4
5
6
[Pd(PPh3)4]
[Pd(PPh3)4]
PdCl2 (+Py 6 mol %) benzene
[RhCl(PPh3)3]
[RhCl(PPh3)3]
benzene
CH3CN
80
80
80
80
19
19
20
24
21
20
0
0
0
0
0
0
Figure 2. ORTEP drawing of [Pd(CN)2(PPh3)2] (50%
probability thermal ellipsoids). All hydrogen atoms are
omitted for clarity. Selected bond lengths (¡) and angles
(deg): Pd(1)-P(1) 2.3313(7), Pd(1)-P(1)¤ 2.3313(7), Pd(1)-
C(1) 2.003(3), Pd(1)-C(1)¤ 2.003(3), P(1)-Pd(1)-P(1)¤
174.94(2), P(1)-Pd(1)-C(1)¤ 92.45(9), P(1)-Pd(1)-C(1)
87.41(9), C(1)-Pd(1)-C(1)¤ 176.85(12).
CH3CN
CH3CN 120
CH3CN 80
[Rh(CO)Cl(PPh3)3]
a) Reaction conditions: catalyst (3 mol %), 1a (1.0 mmol), 4a
(1.0 mmol), solvent (1 mL). b) Determined by H NMR.
1
Table 7. [Co2(CO)8]-Catalyzed Addition of PhSeCN to
1-Octyne in the Presence of COa)
the aromatic substituent, decreasing the coordination ability. In
contrast, aliphatic group on sulfur increases the coordination
ability and makes it possible to bridge both palladium ions.
Bridged thio groups are probably less reactive in comparison
with monodentate thio groups. Accordingly, binuclear palla-
dium complex (complex C) seems less effective for the desired
cyanothiolation in comparison with mononuclear complex
(complex B).
Since the cobalt- or palladium-catalyzed cyanothiolation of
alkynes with thiocyanates was observed, as shown above, it
might be expected that this catalytic system is applicable to the
corresponding organoselenium compounds. Therefore, we next
examined the transition-metal-catalyzed addition reaction of
selenocyanates to alkynes. At first, the reaction of 1-octyne
with phenyl selenocyanate was examined in the presence of
several transition-metal catalysts (Table 6).
When the reaction of 1-octyne with PhSeCN in the presence
of 3 mol % of [Pd(PPh3)4], which is an active catalyst for the
cyanothiolation, was examined, a small amount of diphenyl
diselenide was obtained, but the desired cyanoselenation did
not proceed at all (Entries 1 and 2). Some other palladium and
rhodium complexes such as PdCl2, [RhCl(PPh3)3], and
[Rh(CO)Cl(PPh3)3] were also ineffective (Entries 3-6).
nC6H13
1a
CO
+
+
PhSeCN
4a
nC6H13
PhSe
5a
cat. [Co2(CO)8]
solvent, 120 °C
CN
1a
4a
Time Yield
/h
Entry
Solvent
[E/Z]
/mmol /mmol
/%b)
1
2
3
4
5
6
7
8c)
1
3
10
3
3
10
3
3
1
1
1
1
1
1
1
CH3CN
CH3CN
CH3CN
THF
benzene
benzene
CH2Cl2
CH2Cl2
25
25
25
16
16
18
20
22
7
12
26
10
29
23
38
25
[0/100]
[0/100]
[0/100]
[0/100]
[0/100]
[0/100]
[0/100]
[0/100]
3
a) Reaction conditions: [Co2(CO)8] (3 mol %), solvent (1 mL),
1
CO (3 MPa). b) Determined by H NMR. c) In the absence of
CO.
formed at all but the cyanoselenation product was obtained
with excellent regio- and stereoselectivities, accompanied by
the formation of diphenyl diselenide as a by-product. The
influence of solvents on the cyanoselenation was examined.
Among the solvents employed, polar solvent such as CH3CN
was ineffective (Entries 1-3) and the use of CH2Cl2 was most
effective (Entry 7). On the other hand, the use of excess
PhSeCN led to low yield (7%) (Entry 1). The reaction in the
absence of carbon monoxide resulted in the decrease in yield
(Entry 8). Consequently, the [Co2(CO)8]-catalyzed cyanosele-
nation was found to require pressurized carbon monoxide
(3 MPa) and the use of excess alkyne (Entry 7).
[Pd(PPh3)4]
+ PhSeCN
ð7Þ
[Pd(CN)2(PPh3)2]
benzene, r.t., 24h
Thus, we examined the stoichiometric reaction of PhSeCN
with [Pd(PPh3)4], which afforded not the desired [Pd(CN)-
(PPh3)2(SePh)] but [Pd(CN)2(PPh3)2] (eq 7 and Figure 2). This
is probably because the Pd-Se bond is less stable than the P-S
bond, decomposing to give the diselenide and [Pd(CN)2-
(PPh3)2].
Next, we examined the [Co2(CO)8]-catalyzed reaction of
1-octyne with PhSeCN under several reaction conditions, and
the results are summarized in Table 7. When the [Co2(CO)8]-
catalyzed cyanoselenation was conducted under the pressure of
carbon monoxide, the selenative carbonylation product was not
Conclusion
In summary, the highly regio- and stereoselective [Pd-

160
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
Cyanochalcogenation of Alkynes
(PPh3)4]- and [Co2(CO)8]-catalyzed cyanothiolation of terminal
alkynes with thiocyanates has been disclosed. Oxidative
addition of thiocyanates to the palladium(0) complex was
confirmed by X-ray analysis. In addition, the [Co2(CO)8]-
catalyzed cyanoselenation of terminal alkynes with selenocya-
nates in the pressure of carbon monoxide has been also
developed.
Calcd for C15H19NS: C, 73.42; H, 7.80; N, 5.71%. Found: C,
73.16; H, 7.94; N, 5.25%.
(E)-3-(Phenylthio)-2-nonenenitrile ((E)-3a) (Table 2):
Pale red-brown oil; 1H NMR (300 MHz, CDCl3): ¤ 0.91 (t,
J = 6.6 Hz, 3H), 1.30-1.46 (m, 6H), 1.71 (quint, J = 7.4 Hz,
2H), 2.63 (t, J = 7.8 Hz, 2H), 4.46 (s, 1H), 7.47-7.52 (m, 5H);
13C NMR (68 MHz, CDCl3): ¤ 14.0, 22.5, 28.7, 29.2, 31.4,
35.5, 89.4, 116.9, 128.6, 130.1, 130.4, 135.6, 169.4; IR (NaCl):
3057, 2956, 2929, 2858, 2210 (CN), 1579, 1476, 1466, 1441,
1068, 1024, 790, 751, 705, 691 cm¹1; MS (EI): m/z = 245
(M+, 26). Anal. Calcd for C15H19NS: C, 73.42; H, 7.80; N,
5.71%. Found: C, 73.19; H, 7.80; N, 5.43%.
General Procedure for the [Pd(PPh3)4]-Catalyzed Cyano-
thiolation of Alkynes with Thiocyanates. Method A (the
cyanothiolation in solvents): In a 50 mL stainless steel
autoclave with a magnetic stirring bar under an argon
atmosphere were placed [Pd(PPh3)4] (0.1 mmol), benzene
(1 mL), alkyne (1.0 mmol), and thiocyanate (1.0 mmol). The
vessel was purged three times with argon and then charged at
0.1 MPa. The reaction was conducted with magnetic stirring for
66 h upon heating at 120 °C. After carbon monoxide was
purged, the precipitates were filtered through Celite and
concentrated in vacuo. Purification of the product was carried
out by MPLC eluted with hexane/Et2O.
Method B (the cyanothiolation in the absence of solvents):
In a flame-dried two-necked flask (20 mL) with a reflux
condenser and a magnetic stirring bar under a nitrogen
atmosphere were placed [Pd(PPh3)4] (0.1 mmol), alkyne (1.0
mmol), and thiocyanate (1.0 mmol). The reaction was con-
ducted with magnetic stirring for 20-66 h upon heating at
120 °C. After the reaction was complete, the precipitates were
filtered through Celite and concentrated in vacuo. Purification
of the product was carried out by recycling preparative HPLC
and TLC (PTLC).
(Z)-6-Methyl-3-(phenylthio)-2-heptenenitrile (3b) (Table 5,
Entry 1): Brown oil; 1H NMR (300 MHz, CDCl3): ¤ 0.72 (d,
J = 6.2 Hz, 6H), 1.25-1.40 (m, 3H), 2.15 (t, J = 7.6 Hz, 2H),
5.30 (s, 1H), 7.38-7.52 (m, 5H); 13C NMR (68 MHz, CDCl3): ¤
22.0, 27.3, 34.2, 37.5, 93.3, 116.1, 129.3, 129.3, 129.6, 134.9,
165.9; IR (NaCl): 3059, 2957, 2930, 2869, 2211 (CN), 1573,
1441, 1386, 1368, 1309, 1082, 1069, 1024, 749, 706,
692 cm¹1; MS (EI): m/z = 231 (M+, 8.5). Anal. Calcd for
C14H17NS: C, 72.68; H, 7.41; N, 6.05%. Found: C, 72.33; H,
7.39; N, 5.99%.
Experimental
General. 1H NMR spectra were recorded on JEOL JNM-
GSX 270 (270 MHz), JEOL JNM-AL 400 (400 MHz), or
Varian GEMINI 2000 (300 MHz) spectrometers using CDCl3
as the solvent with Me4Si as the internal standard. 13C NMR
spectra were taken on JEOL JNM-GSX-270 (68 MHz), JEOL
JNM-GSX-400 (100 MHz), or Varian GEMINI 2000 (75 MHz)
spectrometers using CDCl3 as the solvent. 31P NMR spectra
were taken on JEOL-JNM-ECP 500 (202 MHz) spectrometers
1
using CDCl3 as the solvent. Chemical shifts in H NMR were
measured relative to CDCl3 and converted to ¤ (Me4Si) value
by using ¤ (CDCl3) = 7.26. Chemical shifts in 13C NMR were
measured relative to CDCl3 and converted to ¤ (Me4Si) value
by using ¤ (CDCl3) = 77.0. IR spectra were determined on a
Perkin-Elmer Model 1600 spectrometer or JASCO FT/IR-8900
® Fourier Transform Infrared Microsampling System. Mass
spectra were obtained on JEOL JMS-DX303 in the analytical
section of Osaka University. Elemental analyses were per-
formed in the analytical section of Osaka University. Thio-
cyanates were prepared according to the literature.11 Other
materials including phenylselenocyanate were obtained from
commercial supplies and purified by distillation or recrystal-
lization before use. The purification of the products was carried
out by MPLC (silica gel, 25-40 ¯m, length 310 mm, i.d.
25 mm), preparative TLC (PTLC) on Wakogel B-5F silica gel,
or using recycling preparative HPLC (Japan Analytical
Industry Co., Ltd., Model LC-908) equipped with JAIGEL-
1H and -2H columns (GPC) using CHCl3 as an eluent.
Procedure for the [Co2(CO)8]-Catalyzed Cyanothiolation
of 1-Octyne with PhSCN.
In a 50 mL stainless steel
autoclave with a magnetic stirring bar under an argon
atmosphere were placed [Co2(CO)8] (0.1 mmol), CH2Cl2
(1 mL), 1-octyne (1.0 mmol), and phenyl thiocyanate
(1.0 mmol). The vessel was purged three times with carbon
monoxide and then charged at 3 MPa. The reaction was
conducted with magnetic stirring for 11-84 h upon heating at
120-160 °C. After carbon monoxide was purged, the precip-
itates were filtered through Celite and concentrated in vacuo.
Purification of the product was carried out by MPLC eluted
with hexane:Et2O = 4:1, or using a recycling preparative
HPLC (Japan Analytical Industry Co., Ltd., Model LC-908)
equipped with JAIGEL-1H and -2H columns (GPC) using
CHCl3 as an eluent.
(Z)-3-(Phenylthio)-2-nonenenitrile ((Z)-3a) (Table 2):
Pale red-brown oil; 1H NMR (300 MHz, CDCl3): ¤ 0.83 (t,
J = 6.8 Hz, 3H), 1.14-1.25 (m, 6H), 1.39 (quint, J = 7.3 Hz,
2H), 2.15 (t, J = 7.6 Hz, 2H), 5.30 (s, 1H), 7.38-7.51 (m, 5H);
13C NMR (68 MHz, CDCl3): ¤ 13.9, 22.3, 28.2, 28.3, 31.3,
36.2, 93.7, 116.1, 129.4, 129.5, 129.6, 134.9, 165.1; IR (NaCl):
3060, 2958, 2929, 2857, 2212 (CN), 1574, 1441, 1069, 1024,
749, 705, 692 cm¹1; MS (EI): m/z = 245 (M+, 20). Anal.
(Z)-3-(Phenylthio)-2-heptenedinitrile
(3c)
(Table 5,
1
Entry 2): Brown oil; H NMR (300 MHz, CDCl3): ¤ 1.76
(quint, J = 7.0 Hz, 2H), 2.25 (t, J = 7.2 Hz, 2H), 2.36 (t,
J = 7.3 Hz, 2H), 5.41 (s, 1H), 7.35-7.52 (m, 5H); 13C NMR
(68 MHz, CDCl3): ¤ 16.1, 23.8, 34.5, 95.8, 115.4, 118.4, 128.4,
129.7, 130.0, 134.6, 162.3; IR (NaCl): 3048, 2943, 2246 (CN),
2212 (CN), 1573, 1475, 1455, 1441, 1424, 1024, 751, 705,
692 cm¹1; MS (EI): m/z = 229 ([M + H]+, 8.6). HRMS calcd
for C13H13N2S [M + H]+ 229.0799, found 229.0809.
4-Phenyl-3-(phenylthio)-2-butenenitrile [E/Z-Mixture]
(3d) (Table 5, Entry 3):
Pale yellow oil; 1H NMR (300
MHz, CDCl3): ¤ 3.42 (t, J = 0.75 Hz, 2H), 3.95 (s, 2H), 4.58 (s,
1H), 5.11 (t, J = 1.4 Hz, 1H), 6.93-7.49 (m, 20H); 13C NMR
(75 MHz, CDCl3): ¤ 42.2, 77.2, 77.2, 95.2, 95.3, 116.0, 127.4,
128.8, 128.9, 129.1, 129.5, 129.9, 135.4, 135.7, 164.3; IR

T. Ozaki et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 2 (2011)
161
(NaCl): 3061, 3028, 2924, 2210 (CN), 1574, 1495, 1474, 1454,
1441, 1069, 1024, 783, 692 cm¹1; MS (EI): m/z = 251 (M+,
23). HRMS calcd for C16H13NS 251.0770, found 251.0768.
(Z)-3-(1-Cyclohexenyl)-3-(phenylthio)propenenitrile ((Z)-
vacuo. Purification of the product was carried out by MPLC
eluted with hexane:Et2O = 7:3.
(Z)-3-(Phenylseleno)-2-nonenenitrile (5a) (Table 6): Pale
red-brown oil; 1H NMR (270 MHz, CDCl3): ¤ 0.83 (t, J =
6.8 Hz, 3H), 1.11-1.38 (m, 8H), 2.18 (t, J = 7.3 Hz, 2H), 5.60
(s, 1H), 7.33-7.63 (m, 5H); 13C NMR (68 MHz, CDCl3): ¤
13.9, 22.4, 28.2, 28.5, 31.2, 37.9, 96.7, 116.6, 129.4, 130.4,
1
3e) (Table 5, Entry 4): Pale yellow oil; H NMR (300 MHz,
CDCl3): ¤ 1.43-1.72 (m, 4H), 2.16-2.22 (m, 2H), 2.30-2.36
(m, 2H), 4.54 (s, 1H), 6.24 (sept like, J = 1.8 Hz, 1H), 7.42-
7.50 (m, 5H); 13C NMR (75 MHz, CDCl3): ¤ 21.3, 22.2, 25.3,
27.7, 88.0, 117.4, 129.5, 130.0, 130.2, 133.0, 134.0, 135.3,
168.8; IR (NaCl): 3036, 2932, 2858, 2835, 2208 (CN), 1558,
1475, 1441, 748, 706 cm¹1; MS (EI): m/z = 241 (M+, 36).
Anal. Calcd for C15H15NS: C, 74.65; H, 6.26; N, 5.80%.
Found: C, 74.70; H, 6.55; N, 5.29%. HRMS calcd for
C15H15NS 241.0927, found 241.0921.
132.7, 136.4, 165.0; IR (NaCl): 3069, 2966, 2958, 2931, 2862,
¹1
2276 (CN), 1569, 1483, 1353, 741, 690 cm
.
Procedure for the Synthesis of [Pd(CN)(PPh3)2(SPh)]. In
a two-necked flask (20 mL) equipped with a magnetic stirring
bar under a nitrogen atmosphere were placed [Pd(PPh3)4]
(350 mg, 0.25 mmol), benzene (1 mL), and PhSCN (280 mg,
0.25 mmol). The mixture was stirred for 24 h at room temper-
ature. The precipitate was filtered and washed with benzene
to give yellow solid. Recrystallization from C2H4Cl2/benzene
afforded pure trans-[Pd(CN)(PPh3)2(SPh)] (79% yield). Red
solid; mp 229-230 °C; 31P NMR (202 MHz, CDCl3): ¤ 26.22;
IR (KBr): 2130 (CN) cm¹1; Anal. Calcd for C43H35NP2PdS: C,
67.41; H, 4.60; N, 1.83%. Found: C, 68.19; H, 4.66; N, 1.97%.
Crystallographic data have been deposited with Cambridge
Crystallographic Data Centre: Deposition number: CCDC-
800559 for Figure 1, CCDC-800562 for Figure 2. Copies of
data can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html (or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge, CB2 1EZ,
U.K.; Fax: +44 1223 336033; e-mail: deposit@ccdc.cam.
ac.uk).
(E)-3-(1-Cyclohexenyl)-3-(phenylthio)propenenitrile ((E)-
3e) (Table 5, Entry 4):
Yellow oil; 1H NMR (300 MHz,
CDCl3): ¤ 1.47-1.50 (m, 4H), 2.05-2.09 (m, 4H), 5.56 (s, 1H),
6.46 (t, J = 4.1 Hz, 1H), 7.27-7.32 (m, 5H); 13C NMR
(75 MHz, CDCl3): ¤ 21.7, 22.1, 26.0, 26.9, 96.7, 116.9,
127.8, 129.1, 131.3, 133.2, 134.6, 136.5, 161.4; IR (NaCl):
3048, 2932, 2860, 2361, 2210 (CN), 1555, 1479, 1458, 745,
689 cm¹1; MS (EI): m/z = 241 (M+, 110). HRMS calcd for
C15H15NS 241.0927, found 241.0921.
(Z)-3-Phenyl-3-(phenylthio)propenenitrile (3f) (Table 5,
1
Entry 5): Pale yellow oil; H NMR (300 MHz, CDCl3): ¤
5.65 (s, 1H), 7.16-7.44 (m, 10H); 13C NMR (75 MHz, CDCl3):
¤ 77.2, 97.2, 128.3, 128.5, 128.6, 129.1, 130.6, 131.4, 132.6,
136.3, 161.6; IR (NaCl): 2924, 2854, 2210 (CN), 1556, 1441,
745, 691 cm¹1; MS (EI): m/z = 237 (M+, 22). HRMS calcd for
C15H11NS 237.0613, found 237.0609.
This work is supported by Grant-in-Aid for Scientific
Research on Scientific Research (B, No. 19350095), from the
Ministry of Education, Culture, Sports, Science and Technol-
ogy, Japan and also supported by Kyoto-Advanced Nano-
technology Network.
3-(4-Methylphenyl)-3-(phenylthio)propenenitrile [E/Z-
Mixture] (3g) (Table 5, Entry 6): Deep yellow oil; 1H NMR
(300 MHz, CDCl3): ¤ 2.29 (s, 3H), 2.40 (s, 3H), 4.70 (s, 1H),
5.64 (s, 1H), 7.05-7.59 (m, 18H); 13C NMR (75 MHz, CDCl3):
¤ 21.2, 21.3, 89.1, 96.7, 116.6, 117.6, 128.2, 128.4, 129.1,
129.4, 129.6, 130.3, 130.6, 131.7, 132.3, 133.4, 135.4, 141.2,
141.3, 161.2, 166.2; IR (NaCl): 3055, 3020, 2918, 2156 (CN),
1578, 1475, 1439, 810, 737, 687 cm¹1; MS (EI): m/z = 251
(M+, 13). HRMS calcd for C16H13NS 251.0770, found
251.0767.
General Procedure for the Transition-Metal-Catalyzed
Cyanoselenation of 1-Octyne with Selenocyanates. Meth-
od A: In a flame-dried two-necked flask (20 mL) with a reflux
condenser and a magnetic stirring bar under a nitrogen
atmosphere were placed catalyst (0.03 mmol), 1-octyne
(1.0 mmol), and phenyl selenocyanate (1.0 mmol). The reaction
was conducted with magnetic stirring for 19-24 h upon heating
at 80 °C. After the reaction was complete, the precipitates were
filtered through Celite and concentrated in vacuo. Purification
of the product was carried out by MPLC eluted with
hexane:Et2O = 7:3.
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12 Although the role of CO is unclear at present, a possible
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The poisoning of the catalyst may depress the formation of not
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elimination of CO from [Co2(CO)8], inhibiting further oxidative
addition of PhSCN to the catalyst.
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13 When the isolated (Z)-3a (E/Z = 4/96) was heated at

T. Ozaki et al.
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163
150 °C for 84 h in the presence of [Co2(CO)8] catalyst, Z to E
isomerization took place to give 3a with the E/Z ratio of 82/18.
Similarly, upon heating the isolated (Z)-3a (E/Z = 4/96) at 130 °C
for 66 h in the presence of [Pd(PPh3)4] (10 mol %) in benzene, Z to
E isomerization occurred to give 3a with the E/Z ratio of 59/41.
14 In this reaction, the starting materials were consumed, and
some by-products were also obtained, e.g., the (PhS)2 adduct to
1-octyne.
[PtH(SePh)(PPh3)2] for hydroselenation of alkynes: See, Ref. 4m.
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17 Recent theoretical studies for the palladium-catalyzed
cyanothiolation suggest the following: i) Oxidative addition takes
place between the S-CN bond in preference to the C-SCN bond;
ii) Alkyne insertion takes place between the S-Pd bond in
preference to the Pd-CN bond; iii) Thiopalladation takes place to
introduce the thio group into the inner position of alkyne not the
terminal position.
15 Since complex B is trans-isomer, trans to cis isomerization
is required for reductive elimination of the product. Beletskaya and
Ananikov suggested the trans to cis isomerization of trans-