Nickel/Lewis acid-catalyzed aryl-and alkenylcyanation of unsaturated bonds

Article abstract of DOI:10.1246/bcsj.20100068

Lewis acid cocatalysts such as organoaluminum and-boron compounds dramatically improve the efficiency of the nickel-catalyzed arylcyanation of alkynes. Electron-rich aryl cyanides, which exhibit poor reactivity in the absence of Lewis acids, smoothly unde

Full text of DOI:10.1246/bcsj.20100068

1170 Bull. Chem. Soc. Jpn. Vol. 83, No. 10, 1170–1184 (2010)
© 2010 The Chemical Society of Japan
Nickel/Lewis Acid-Catalyzed Aryl- and Alkenylcyanation
of Unsaturated Bonds
Akira Yada, Shiro Ebata, Hiroaki Idei, Di Zhang, Yoshiaki Nakao,* and Tamejiro Hiyama*,³
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510
Received March 10, 2010; E-mail: yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
Lewis acid cocatalysts such as organoaluminum and -boron compounds dramatically improve the efficiency of the
nickel-catalyzed arylcyanation of alkynes. Electron-rich aryl cyanides, which exhibit poor reactivity in the absence of
Lewis acids, smoothly undergo the arylcyanation reaction under the nickel/Lewis acid dual catalysis. Excellent
chemoselectivity is observed for aryl cyanides having a chloro or bromo group, which allows a single-step access to a
synthetic intermediate of P-3622, a squalene synthetase inhibitor. The scope of the arylcyanation is also expanded to
norbornadiene. Alkenylcyanation of alkynes is achieved under the nickel/Lewis acid dual catalysis to give cyano-
substituted 1,3-dienes stereoselectively.
Cleavage of the carbon-cyano bond in nitriles followed by
addition reaction of the resulting two organic fragments across
unsaturated bonds by transition-metal catalysis should provide
us with a revolutionary synthetic method, because such
transformation allows simultaneous construction of carbon-
carbon and carbon-cyano bonds without forming by-products.
The reaction, called carbocyanation, was recently achieved
using nickel1 and palladium2,3 catalysts. Compared to palla-
dium-catalyzed reactions, nickel catalysis allows a wide variety
of nitriles including aryl,1a,1d,1e alkoxycarbonyl,1c,1g allyl,1b,1i
and alkynyl1h cyanides to participate in the carbocyanation
reaction. Nevertheless, the reactions still require generally high
catalyst loadings and harsh reaction conditions. For example,
arylcyanation of alkynes using electron-rich aryl cyanides is
feasible but generally sluggish: addition of 4-methoxybenzo-
nitrile (1a) across 4-octyne (2a) in the presence of 10 mol % of
a Ni/PMe3 catalyst at 100 °C took 111 h for completion to give
the corresponding adduct 3aa in 54% yield, whereas that of
methyl 4-cyanobenzoate (1d), an electron-deficient one, gave
the adduct 3da in 96% yield after 24 h (eq 1).1a,1d Moreover,
highly electron-rich 4-dimethylaminobenzonitrile (1f) totally
failed to give product 3fa (eq 1).
addition6 and reductive elimination7 of C-CN bonds, the effect
of LA catalysts on the arylcyanation reaction of alkynes is
investigated in this paper to disclose that the scope of aryl
cyanides for the reaction with alkynes and norbornadiene is
expanded significantly under the nickel/LA cooperative catal-
ysis. The cooperative bimetal catalysis allows the addition
reaction of alkenyl cyanides across alkynes, giving 1-cyano-
1,3-dienes with high regio- and stereoselectivities.8,9
Results and Discussion
Effect of Lewis Acid Cocatalyst on Nickel-Catalyzed
Arylcyanation of Alkynes. We first assessed the effect of
various LA catalysts together with Ni(cod)2 (5 mol %) and
PMe3 (10 mol %) as a ligand on the reaction of aryl cyanide
(1a, 1.0 mmol) with 4-octyne (2a, 1.0 mmol) in toluene at
50-80 °C. The results are summarized in Table 1. Of LAs
examined, aluminum, boron, and zinc were found to signifi-
cantly promote the reaction, giving (Z)-3aa in good to excellent
yields at 80 °C (Entries 3, 5, 10, 12, 17, 19, and 26), whereas
the absence of the LA catalysts gave (Z)-3aa in lower yields
even at 80 °C (Entries 1 and 2). AlMeCl2 was also found
effective for the reaction, but a significant amount of (E)-3aa
was observed at 80 °C probably through isomerization of
initially formed (Z)-3aa (Entry 7). Strong Lewis acidity
appears to be responsible for such isomerization (vide infra).
Some LAs including AlMe3, AlMe2Cl, AlMeCl2, and BEt3 are
still effective even at 50 °C (Entries 4, 6, 8, and 18). In the case
of ZnCl2, formation of insoluble materials was observed after
the reaction at 50 °C (Entry 27). Ti(OiPr)4, MgBr2, LaCl3,
and Me3SiOTf were less effective (Entries 29-32). Other LAs
including indium, copper, iron, cobalt, gold, and zirconium
LAs inhibited the reaction. Finally, we tested various combi-
nations of LAs and ligands in the presence of 1 mol % of
Ni(cod)2 to find that ligands such as PPhMe2, PPh2Me, and
PPh2Cy give generally better results than PMe3. For example,
the combination of PPh2Me/AlMe3 or BPh3 gave (Z)-3aa in
over 90% yield with only a trace amount of (E)-3aa (Table 2).
Ni(cod)2 (10 mol %)
PMe3 (20 mol %)
Ar
Pr
CN
+
ð1Þ
Ar CN
Pr
Pr
toluene, 100 °C
Pr
2a
Ar = 4-MeO−C6H4 (1a)
Ar = 4-MeO−C6H4 (3aa):
54% (111 h)
4-MeO2C−C6H4 (1d)
4-Me2N−C6H4 (1f)
4-MeO2C−C6H4 (3da): 96% (24 h)
4-Me2N−C6H4 (3fa):
0%
Based on the mechanism of the nickel-catalyzed arylcyana-
tion reaction suggested by theoretical calculations,4 oxidative
addition of the C-CN bond to nickel(0) is likely rate-
determining: an elemental step that proceeds through ©2-nitrile-
and ©2-arenenickel complexes.5 As Lewis acids (LAs) have
been known to accelerate elemental steps such as oxidative
³ Present address: Research and Development Initiative, Chuo
University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551
Published on the web September 16, 2010; doi:10.1246/bcsj.20100068

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1171
Table 1. Effect of LA Cocatalyst on Nickel-Catalyzed
Arylcyanation of 2a with 1aa)
Table 2. Optimization of a Combination of a LA and a
Ligand for the Reaction of 1a across 2aa)
MeO
MeO
+
Pr
Pr
Ni(cod)2 (5 mol %)
PMe3 (10 mol %)
LA (20 mol %)
MeO
CN
1a (1.0 mmol)
CN
1a (1.0 mmol)
2a (1.0 mmol)
+
CN
Pr
toluene, 50−80 °C, 24 h
Pr
Pr
2a (1.0 mmol)
Ni(cod)2 (1 mol %)
ligand (2 mol %)
LA (4 mol %)
MeO
Pr
(Z )-3aa
Yield/%b)
CN
Pr
toluene, 50 °C, 24 h
Entry
Lewis acid
Temp/°C
(Z)-3aa
(E)-3aa
Pr
1
2
3
4
5
6
7
8
9
none
none
AlMe3
AlMe3
AlMe2Cl
AlMe2Cl
AlMeCl2
AlMeCl2
AlCl3
AlPh3¢OEt2
AlPh3¢OEt2
MADc)
MADc)
Al(OiPr)3
Al(OPh)3
Al(OTf)3
BEt3
BEt3
BPh3
80
50
80
50
80
50
80
50
80
80
50
80
50
80
80
80
80
50
80
50
80
80
80
80
80
80
50
80
80
80
80
80
36
7
1
0
6
0
21
1
50
4
0
3
0
10
1
6
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
4
3
4
(Z)-3aa
LA/yield of (Z)-3aa/%b)
AlMe3 AlMe2Cl AlMeCl2 BPh3 BEt3
91
61
79
94
41
82
6
90
47
82
7
48
0
0
88
82
68
37
17
1
0
8
2
86
68
61
42
54
39
21
Ligand
PMe3
P(n-Bu)3
PPhMe2
PPh2Me
PPh2Cy
P(4-MeO-C6H4)3
Ph2P(CH2)6PPh2
60
63
95
92
95
29
72
88
41
>99
98
50
6
7
5
8
<1
<1
<1
<1
31
39
78
92
79
53
60
9
<1
6
<1
1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
1
<1
66
a) All the reactions were carried out using 1a (1.0 mmol), 2a
(1.0 mmol), Ni(cod)2 (10 ¯mol), ligand (20 ¯mol), and LA
(40 ¯mol) in toluene (1.0 mL) at 50 °C for 24 h. b) Estimated
by GC using dodecane as an internal standard.
MeO
MeO
BPh3
(PhMe2P)2NiCl2 (1 mol %)
AlMe3 (4 mol %)
CN
1a (1.0 mmol)
B(C6F5)3
BF3¢OEt2
ZnEt2
ZnPh2
Zn(C6F5)2
ZnCl2
CN
Pr
+
toluene, 50 °C, 19 h
Pr
Pr
Pr
(Z)-3aa, 96%
2a (1.0 mmol)
2 AlMe3
ZnCl2
P
P
Cl
Cl
P
P
Me
Me
P
Ni
Ni
Ni0
P
Zn(OTf)2
Ti(OiPr)4
MgBr2¢OEt2
LaCl3
2 AlMe2Cl
Me−Me
P = PMe2Ph
Scheme 1. The reaction of 1a with 2a using dichlorobis-
(dimethylphenylphosphine)nickel(II) as a precatalyst.
Me3SiOTf
a) All the reactions were carried out using 1a (1.0 mmol), 2a
(1.0 mmol), Ni(cod)2 (50 ¯mol), PMe3 (100 ¯mol), and Lewis
acid (200 ¯mol) in toluene (1.0 mL) for 24 h. b) Estimated by
GC using dodecane as an internal standard. c) Methylalumi-
num bis(2,6-di-tert-butyl-4-methylphenolate).
those unreactive under the LA-free conditions (Table 3). Under
the optimized conditions, p-tolunitrile (1b) and benzonitrile
(1c) also smoothly added across 2a in good to excellent yields
in one day (Entries 2 and 3). Functional groups such as an ester
and THP-protected [2-(hydroxymethyl)phenyl]dimethylsilyl
group10 tolerated the reaction conditions (Entries 4 and 5).
More electron rich nitriles, 4-dimethylamino- (1f) and 4-
diphenylaminobenzonitrile (1g), underwent the arylcyanation
to give the corresponding adducts in good yields in one or two
days (Entries 6 and 7). It is noteworthy that the Ar-CN bonds
of 4-bromo- (1h), 4-chloro- (1i), and 4-fluorobenzonitrile (1j)
were selectively activated over the Ar-halogen bonds, giving
arylcyanation products in good to excellent yields (Entries 8-
10). Even the sterically highly demanding aryl cyanides like
2-methoxybenzonitrile (1k) and 2,6-dimethylbenzonitrile (1l)
From a practical view point, it is worth noting that a similar
catalyst prepared in situ from air- and moisture-stable
(PhMe2P)2NiCl2 (1 mol %) and AlMe3 (4 mol %) effected the
reaction to give (Z)-3aa in 96% yield after 19 h. In the reaction
course, the Ni(II) catalyst is reduced to a catalytically active
Ni(0) species and simultaneously coproduced AlMe2Cl as the
LA cocatalyst (Scheme 1).
Nickel/Lewis Acid-Catalyzed Arylcyanation of Alkynes.
The new catalyst systems thus tuned were then applied to the
arylcyanation of 2a using various aryl cyanides especially

1172 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
Table 3. Nickel/Lewis Acid-Catalyzed Arylcyanation of 4-Octyne (2a)a)
Ni(cod)2 (1 mol %)
ligand (2 mol %)
conditions:
A: PPhMe2 and AlMe2Cl
B: PPh2Cy and AlMe3
Ar
CN
R2
LA (4 mol %)
+
Ar CN
Pr
Pr
toluene
R1
C: Ph2P(CH2)4PPh2 and BPh3
3
1 (1.0 mmol)
2a (1.0 mmol)
Entry
Aryl cyanide
Cond.
A
Temp/°C
Time/h
Product, yield/%b)
MeO
Me
MeO
Me
CN
1
1a
50
16
3aa, 96
Pr
CN
CN
Pr
CN
2
3
4
1b
1c
1d
A
B
A
60
50
80
20
16
25
3ba, 72
Pr
Pr
CN
3ca, 97
Pr
CN
Pr
MeO2C
ArMe2Si
Me2N
Ph2N
Br
MeO2C
ArMe2Si
Me2N
Ph2N
Br
CN
Pr
3da, 93
3ea, 90
3fa, 87
3ga, 91
3ha, 72
3ia, 94
CN
Pr
CN
Pr
5
1ec)
1f
B
A
B
A
B
50
80
50
50
50
42
21
47
27
18
CN
Pr
CN
Pr
6
CN
Pr
CN
Pr
7
1g
1h
1i
CN
Pr
CN
Pr
8d)
CN
Pr
Pr
Pr
Cl
Cl
CN
Pr
9
CN
CN
F
F
CN
Pr
10
1j
B
B
A
B
50
80
18
28
3ja, 95
3ka, 92
3la, 78
3ma, 81
CN
Pr
11
1k
1l
CN
OMe
OMe Pr
Me
CN
Me
CN
12d)
13
100
50
134
140
Pr
Me
S
Me Pr
CN
Pr
1m
S
CN
Pr
Continued on next page:

A. Yada et al.
Continued:
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1173
Entry
Aryl cyanide
Cond.
A
Temp/°C
Time/h
Product, yield/%b)
CN
CN
14
1n
1o
1p
50
116
5
3na, 58
3oa, 83f)
3pa, 91
MeN
Pr
Pr
N
Me
CN
15e)
16g)
B
C
80
80
Fe
CN
Fe
Pr
Pr
O
O
CN
20
O
Pr
O
CN
Pr
CN
Pr
17g)
1q
C
80
20
3qa, 92
O
O
CN
O
Pr
O
a) Condition A, PPhMe2 and AlMe2Cl; condition B, PPh2Cy and AlMe3; condition C, Ph2P(CH2)4PPh2 and BPh3.
b) Isolated yields. c) Ar = 2-(THPOCH2)C6H4. d) The reaction was carried out using Ni(cod)2 (50 ¯mol), PPhMe2
(100 ¯mol), and AlMe2Cl (200 ¯mol). e) The reaction was carried out using Ni(cod)2 (50 ¯mol), PPh2Cy
(100 ¯mol), and AlMe3 (200 ¯mol). f) (Z)/(E) = 92:8. g) The reaction was carried out using Ni(cod)2 (40 ¯mol),
Ph2P(CH2)4PPh2 (40 ¯mol), and BPh3 (160 ¯mol).
participated in the reaction, although higher reaction temper-
atures (80-100 °C), higher loadings of catalysts, and/or
prolonged reaction time were required (Entries 11 and 12).
Heteroaryl cyanides also successfully added across 2a (Entries
13-17). The selective activation of an Ar-CN bond over
the C(2)-H bond in 1-methyl-3-cyanoindole (1n) exhibits
another chemoselective feature of the present Ni-LA catalysis
(Entry 14), whereas the Ar-H bond was activated in the
absence of LA.11 Cyanoferrocene (1o) also participated in
the reaction efficiently, although a mixture of stereoisomers
resulted due possibly to isomerization of the initially formed
cis-adduct to trans-adduct (Entry 15). Indeed, exposure of the
isolated sample of (Z)-3oa to the present reaction conditions
caused the isomerization. Heteroaryl cyanides such as 3-
cyanochromone (1p) and 3-cyanocoumarin (1q) were futile
under the Ni/Al catalyst system, whereas Ni/BPh3 effected the
reactions to give adducts in good yields (Entries 16 and 17).
The scope of internal alkynes was next examined with 4-
chlorobenzonitrile (1i) (Table 4). Symmetric alkynes such as
2-butyne (2b), 3-hexyne (2c), and 1,4-bis(trimethylsilyl)-2-
butyne (2d) all participated in the reaction to give products
in good yields (Entries 1-3). An unsymmetrical alkyne, 4,4-
dimethyl-2-pentyne (2f), gave the corresponding adduct 3if
with good regioselectivity (Entry 5), whereas 4-methyl-2-
pentyne (2e) gave modest selectivity (Entry 4). All the reaction
gave the corresponding adducts having a larger substituent
at the cyano-substituted carbon as major products. Internal
alkynes with aryl- and silyl-substituents reacted with 1i
successfully with similar regioselectivity, although significant
amounts of trans-adducts were also obtained probably through
isomerization of the initial cis-adducts as evidenced by time-
dependent E/Z ratios (Entries 6-8). The excellent chemo-
selectivity of the present Ni-LA catalysis provided a single step
preparation of 3ii, which is a synthetic intermediate of P-3622,
a squalene synthetase inhibitor (Entry 8).12 Under the same
catalyst system, terminal alkynes failed to give the correspond-
ing product due to rapid trimerization and/or oligomerization.
Nickel/AlMe2Cl-Catalyzed Arylcyanation of Norborna-
diene. We next turned our attention to application of the Ni/
LA system to arylcyanation of norbornadiene (4), which under
the original LA-free conditions reacted only with electron-
deficient aryl cyanides.13 The reaction of 1a with 4 in the
presence of the Ni/AlMe2Cl catalyst with Me2P(CH2)2PMe2
(DMPE) as a ligand in toluene at 80 °C for 4.5 h proceeded
successfully to afford exo-cis-arylcyanation product 5a in 69%
yield (Entry 1 of Table 5). Monodentate phosphine and biden-
tate DPPE ligand were totally ineffective. The same catalyst
system was further applied to the reactions of a wide variety of
aryl cyanides, especially impotent cyanides in the absence of
LA, to give the corresponding adducts in good yields (Entries 2-
7). No double addition products were detected in any case,
whereas norbornene was demonstrated previously to undergo
the addition of aryl cyanides in the absence of LA catalysts.1e
The resulting norbornene derivatives 5 would find further
applications as precursors for functionalized cyclopentanes1e or
as monomers for ring-opening metathesis polymerization.14
Nickel/BPh3-Catalyzed Alkenylcyanation of Alkynes.
We then turned our attention to the reaction of alkenyl
cyanides with alkynes. After a brief optimization of conditions
for the reaction of (E)-cinnamonitrile (6a) with 4-octyne
(2a), we found that the combination of Ni(cod)2 (2 mol %),
PMe3 (4 mol %), and BPh3 (8 mol %) was effective to give
the alkenylcyanation product, dienenitrile 7aa, in 94% yield
(Entry 1 of Table 6). LAs such as AlMe3 and AlMe2Cl were

1174 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
Table 4. Nickel/AlMe2Cl-Catalyzed Arylcyanation of Internal Alkynes with 1i
Ni(cod)2 (5 mol %)
PPh2(i-Pr) (10 mol %)
AlMe2Cl (20 mol %)
Cl
Cl
Cl
R1
R2
+
+
CN
R2
NC
R1
toluene, 60 °C
CN
1i (1.0 mmol)
R1
R2
3'
2 (1.0 mmol)
3
Entry
1
Alkyne
Time/h
Product(s), yield(s)/%a) (3/3¤)b)
Cl
Me
Me
CN
Me
12
88
92
84
2b
Me
3ib
Cl
Et
Et
CN
Et
2
6
2c
Et
3ic
Cl
Me3Si
SiMe3
CN
3
6
2d
2e
Me3Si
SiMe3
3id
Cl
Cl
Cl
Cl
Cl
Cl
Me
i-Pr
+
CN
iPr
NC
Me
4
5
87 (64:36)
Me
Me
Et
iPr
3ie + 3′ie
Me
t-Bu
+
CN
tBu
NC
Me
5
19
32
89 (91:9)
2f
2g
2h
tBu
3if + 3′if
Et
p-Anis
+
6c)
3ig, 53d), 3¤ig, 27
CN
NC
Et
p-Anis
p-Anis
3ig, 3′ig
Cl
Cl
Cl
Me
SiMe3
+
7e)
13
37
3ih, 70f), 3¤ih, 9
CN
SiMe3
NC
Me
Me
SiMe3
Cl
3ih, 3′ih
p-Anis
SiMe3
+
8g)
3ii, 73h), 3¤ii, <5
CN
NC
2i
p-Anis
SiMe3
p-Anis
SiMe3
3ii, 3′ii
1
a) Isolated yields. b) Determined by H NMR analysis. c) PPh2Me was used as a ligand. d) (E)-3ig was also
obtained in 5% yield. e) Reaction run at 80 °C. f) E/Z = 59:41 (78:22 at 5 h). g) Reaction run with 1 mol % of
catalyst. h) E/Z = 47:53 (57:43 at 12 h).

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1175
Table 5. Nickel/AlMe2Cl-Catalyzed Arylcyanation of
Norbornadiene (4)a)
with 3 equivalents of 2a gave double alkenylcyanation product
7fa in 84% yield (eq 2).
Ni(cod)2 (1 mol %)
DMPE (1 mol %)
AlMe2Cl (4 mol %)
NC
Ni(cod)2 (4 mol %)
PMe3 (8 mol %)
BPh3 (16 mol %)
Ar
NC
+
Ar CN
CN
toluene, 80 °C
6f (1.0 mmol)
5
1 (1.0 mmol)
4 (1.5 mmol)
Time
+
toluene, 80 °C, 44 h
Pr
Pr
Aryl
cyanide
Yield
/%b)
Entry
1
Product
2a (3.0 mmol)
/h
Pr
Pr
MeO
Me
CN
Pr
ð2Þ
1a
4.5
69
70
68
57
59
69
5a
5b
5c
5f
CN
NC
Pr
7fa, 84%
2
1b
1c
1f
2
2
2
NC
Obtained substituted 2,4-pentadienenitriles 7 were readily
converted to substituted pyridines via reduction with DIBAL-H
and 6³ electrocyclization followed by aerobic oxidation as
exemplified by the reaction of 7aa (eq 3).
3
NC
Me2N
Br
4c)
5
Ph
Ph
Ph
1) DIBAL−H
toluene, 0 °C
2) MeOH, 0 °C
NH
N
NC
CN
Pr
H
ð3Þ
100 °C
open air
(− H2)
1h
1i
10
5h
5i
Pr
Pr
Pr
Pr
Pr
NC
7aa
8
61%
Cl
6
2
Reaction Mechanism of Aryl- and Alkenylcyanation
Reactions. A six-step catalytic cycle shown in Scheme 2
seems most probable, which starts with (1) formation of
LA-bonded ©2-nitrile nickel intermediate A;9c (2) oxidative
addition of C-CN bonds of aryl or alkenyl cyanides to
nickel(0) giving aryl- or alkenylnickel intermediate B; (3)
formation of five-coordinate nickel intermediate C; (4) sub-
sequent ligand exchange (path A); (5) migratory insertion of
alkynes into the R-Ni bond of D to give E; (6) reductive
elimination to finally give rise to carbocyanation products and
regenerate nickel(0) species and LA.4 In the case of norborna-
diene, its migratory insertion would take place directly from
five-coordinate nickel C to give E (path B) because of the use
of a chelating bisphosphine. The observed dramatic effects of
LA catalysis is attributed primarily to acceleration of oxidative
addition of C-CN bonds by coordination of a cyano group to
the LA catalyst as expected.6 LA may also facilitate reductive
elimination of C-CN bonds7 and/or other elemental steps.
Coordination of an alkyne to a nickel center in the direction to
minimize steric repulsion between bulkier R2- and aryl or
alkenyl groups (D) should be responsible for the observed
regioselectivity as was the case for the LA-free reaction.1d
Trans adducts may be derived from phosphine- and/or heat-
mediated isomerization of the initial cis adducts, as the
stereoisomeric ratios depended on the reaction time and
conditions. Stronger Lewis acid appears to more induce such
isomerization. A silyl group tends to further facilitate such
isomerization.1d In the case of aryl-substituted alkynes,
alkenylnickel species E may isomerize to its isomer F possibly
through conjugated addition of phosphine ligand15 followed by
reductive elimination to give trans adducts.
NC
OMe
7
1k
5.5
58
5k
NC
a) All the reactions were carried out using 1 (1.0 mmol),
4 (1.5 mmol), Ni(cod)2 (10 ¯mol), DMPE (10 ¯mol), and
AlMe2Cl (40 ¯mol) in toluene (670 ¯L). b) Isolated yields.
c) Reaction run at 100 °C.
also effective for the reaction, but were accompanied by a
significant amount of 2E-isomer. It is noteworthy that the
catalyst differentiates precisely the alkenyl-CN bonds of
starting alkenyl cyanides from those of products probably
due to steric and/or electronic factors. Under the same reaction
conditions, acrylonitrile failed to participate in the reaction,
giving a complex mixture. The reaction of (Z)-2-pentenenitrile
(6b) resulted in contamination of its 4E-isomer, possibly
because partial isomerization of 6b to (E)-2-pentenenitrile took
place before the addition reaction (Entry 2). Disubstituted
acrylonitriles gave tetrasubstituted 2,4-pentadienenitriles in
good yields (Entries 3-5). Especially worth noting is selective
activation of the cyano group trans to the phenyl group in
benzylidenemalononitrile (6e) to give dicyanosubstituted 1,3-
diene 7ea. Alkenylcyanation of unsymmetrical alkynes were
also examined. Whereas the regioselection across 4-methyl-2-
pentyne (2e) was modest (Entry 6), trimethyl(1-propynyl)silane
(2h) and 1-phenyl-1-propyne (2j) reacted highly regioselec-
tively to give adducts (Entries 7 and 8). In contrast to our
expectation, the observed regioselectivity of the reaction
with 2h or 2j was opposite to the addition reaction of aryl
cyanide with unsymmetrical alkynes (Table 4). This reversal
of regioselectivity might be ascribed to the difference of the
ligand. However any of several alternative explanations may be
possible. The reaction of 6f with two alkenyl cyanide moieties
Conclusion
In summary, we have demonstrated a dramatic effect of LA
catalysts on nickel-catalyzed arylcyanation of alkynes and

1176 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
Table 6. Nickel/BPh3-Catalyzed Alkenylcyanation of Alkynesa)
Ni(cod)2 (2 mol %)
PMe3 (4 mol %)
BPh3 (8 mol %)
R3
R4
R5
R5
R3
R4
R3
R4
R5
CN
R2
NC
R1
R2
+
+
toluene, 80 °C
CN
R1
7
R1
R2
7'
6 (1.0 mmol)
2
Entry Alkenyl cyanide Alkyne (mmol)
Time/h
Product(s), yield/%b)
Ph
CN
Ph
Pr
Pr
CN
1
20
94
2a (1.2)
Pr
Pr
6a
7aa
CN
Pr
CN
Et
Et
2
3
2a (1.2)
2a (1.2)
15
21
78c)
91
Pr
7ba
6b
CN
CN
CN
Pr
7ca
Pr
6c
Ph
Ph
Ph
Ph
CN
Pr
4
2a (1.2)
2a (1.2)
46
13
3
94
Ph
Pr
7da
6d
Ph
CN
CN
CN
CN
Pr
5d)
81e)
Pr
7ea
6e
Ph
Ph
CN
NC
Me
i-Pr
+
6f)
6a
7ae, 44, 7¤ae, 37
2e (2.0)
Me
i-Pr
Me
i-Pr
7ae + 7′ae
Ph
NC
Me
SiMe3
7f)
6a
6a
15
6
66g)
Me
SiMe3
2h (2.0)
7′ah
Ph
NC
Me
Me
Ph
8f)
35
2j (2.0)
Ph
7′aj
a) All the reactions were carried out using 6 (1.0 mmol), 2 (1.2-2.0 mmol), Ni(cod)2 (20-50 ¯mol), PMe3 (40-
100 ¯mol), and BPh3 (80-200 ¯mol) in toluene (1.0 mL) at 80 °C. b) Isolated yields isomerically pure products.
c) 4Z/4E = 84:16. d) The reaction was carried out using Ni(cod)2 (40 ¯mol), Ph2P(CH2)4PPh2 (40 ¯mol), and BPh3
(160 ¯mol). e) An isomer was also obtained in µ2% yield. f) The reaction was carried out using Ni(cod)2
(50 ¯mol), PCyPh2 (100 ¯mol), and BPh3 (200 ¯mol). g) A mixture of isomers was also obtained in µ7% yield.
norbornadiene. Lewis acids such as organoaluminum and
-boron compounds significantly accelerate the whole catalytic
cycle of the arylcyanation reaction to allow expansion of the
scope of aryl cyanides. Also demonstrated is the first example
of the addition reaction of alkenyl cyanides across alkynes by
the Ni/BPh3 cooperative catalysis to give variously substituted
2,4-dienenitriles stereoselectively.
sensitive materials were conducted with standard Schlenk
technique or in a dry box under an argon or nitrogen
atmosphere. Flash column chromatography was performed
using Kanto Chemical silica gel (spherical, 40-50 ¯m).
Analytical thin layer chromatography (TLC) was performed
on Merck Kieselgel 60 F254 (0.25 mm) plates. Visualization
was accomplished with UV light (254 nm) and/or an aqueous
alkaline KMnO4 solution followed by heating. Proton and
carbon nuclear magnetic resonance spectra (1H NMR and
13C NMR) were recorded on a Varian Mercury 400 spectrom-
Experimental
General.
All manipulations of oxygen- and moisture-

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1177
L or heat
(cat. LA)
R2
CN
R
R
R2
CN
NC R
R1
R1
L
L
trans-adduct
cis-adduct
Ni(0)
+
LA
R
R
L
R2
L
N C
Ni
L
LA
R
reductive
elimination
Ni
R1
CN−LA
CN−LA
L
L
Ni
L
R2 = Ar
R1
R2
A
L
R = aryl or alkenyl
E
F
L = phosphine ligand
LA = AlMe3, AlMe2Cl, BPh3
oxidative
addition
migratory
insertion
L
L
R
R
L
R1
Ni
path B
Ni
CN−LA
L
CN−LA
R2
D
B
R
R1
path A
L
R1
R2
L
Ni CN−LA
L
R2
ligand
substitution
C
Scheme 2. Plausible reaction mechanism.
eter with solvent resonance as the internal standard (1H NMR,
added a drop of a 12 M HCl aqueous solution, and the whole
was stirred for 10 min before addition of additional 4-
1
CHCl3 at 7.26 ppm; 13C NMR, CDCl3 at 77.0 ppm). H NMR
data are reported as follows: chemical shift, multiplicity
(s = singlet, d = doublet, t = triplet, q = quartet, quint =
quintet, sext = sextet, br = broad, m = multiplet), coupling
cyanophenyl[(2-hydroxymethyl)phenyl]dimethylsilane
(525
mg, 2.0 mmol) at rt. The reaction mixture was stirred at rt for
12 h and concentrated in vacuo to give a residue, which was
purified by recrystallization from hexane-ethyl acetate (9:1) to
give 1e (772 mg, 55%) as a colorless solid, mp 59.8-60.8 °C,
Rf = 0.25 (hexane-ethyl acetate = 5:1). 1H NMR (400 MHz,
CDCl3): ¤ 0.62 (s, 3H), 0.63 (s, 3H), 1.40-1.65 (m, 5H), 1.70-
1.81 (m, 1H), 3.41 (m, 1H), 3.73 (distorted td, J = 9.8, 3.1 Hz,
1H), 4.32 (d, J = 11.9 Hz, 1H), 4.43 (t, J = 3.5 Hz, 1H), 4.62
(d, J = 11.9 Hz, 1H), 7.31 (td, J = 7.3, 1.5 Hz, 1H), 7.44
(td, J = 7.4, 1.3 Hz, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.51 (dd,
J = 7.4, 1.0 Hz, 1H), 7.61 (m, 4H); 13C NMR (101 MHz,
CDCl3): ¤ ¹1.2, ¹1.1, 19.4, 25.5, 30.5, 62.1, 68.7, 97.7, 112.4,
118.9, 126.9, 128.7, 130.0, 130.8, 134.30, 134.35, 135.3,
143.9, 146.0. IR (KBr): 3470, 3051, 2942, 2864, 2226, 1937,
1589, 1566, 1543, 1493, 1464, 1451, 1437, 1414, 1400, 1385,
1350, 1321, 1314, 1281, 1254, 1200, 1184, 1163, 1155, 1128,
1117, 1098, 1078, 1055, 1032, 974, 909, 887, 870, 829, 826,
802, 781, 758, 748, 721, 689, 656, 557, 530, 496, 459, 444,
436 cm¹1. Anal. Calcd for C21H25NO2Si: C, 71.75; H, 7.17%.
Found: C, 71.75; H, 7.17%.
1,4-Bis(¢-cyanovinyl)benzene (6f). To a solution of NaH
(756 mg, 32 mmol) in THF (60 mL) was added diethyl
cyanomethylphosphonate (5.6 g, 32 mmol) dropwise at 0 °C,
and the whole was stirred for 30 min. To this was added
dropwise a solution of terephthalaldehyde (2.0 g, 15.0 mmol) in
THF (10 mL), and the resulting mixture was stirred for 18 h
before addition of water (100 mL) at rt. The organic layer was
separated; the aqueous layer was extracted three times with
diethyl ether. The combined organic layers were washed twice
with water and brine, dried over anhydrous MgSO4, filtered
through a Celite pad, and concentrated in vacuo. The residue
constants (Hz), and integration. Infrared spectra (IR) recorded
¹1
on a Shimadzu FTIR-8400 spectrometer are reported in cm
.
Melting points (mp) were determined using a YANAKO
MP-500D. Elemental analyses were performed by Elemental
Analysis Center of Kyoto University. High-resolution mass
spectra were obtained with a JEOL JMS-700 (EI). Preparative
recycling gel permeation chromatography (GPC) and recycling
silica gel chromatography were performed with a JAI LC-908
chromatograph equipped with JAIGEL-1H and -2H (chloro-
form as an eluent) or COSMOSIL 5SL-II (hexane-ethyl acetate
as an eluent), respectively. GC analysis was performed on a
Shimadzu GC 2014 equipped with an ENV-1 column (Kanto
Chemical, 30 m © 0.25 mm, pressure = 31.7 kPa, detector =
FID, 290 °C) with helium gas as a carrier.
Chemicals. Unless otherwise noted, commercially avail-
able chemicals were distilled and degassed before use. Ni(cod)2
was purchased from Strem and used without further purifica-
tion. Anhydrous toluene was purchased from Kanto Chemical
and degassed by purging vigorously with argon for 20 min and
further purified by passage through activated alumina under
positive argon pressure as described by Grubbs et al.16 Aryl
cyanides 1g,17 1n,11 and 1o,18 alkynes 2d19 and 2g,20 alkenyl
cyanides 6c21 and 6e,22 and dichlorobis(dimethylphenylphos-
phine)nickel(II)23 were prepared according to the respective
literature procedure.
4-Cyanophenyl-[2-(tetrahydro-2H-pyran-2-oxymethyl)-
phenyl]dimethylsilane (1e).
To a mixture of 4-cyano-
phenyl[(2-hydroxymethyl)phenyl]dimethylsilane (525 mg, 2.0
mmol)24 and 3,4-dihydro-2H-pyran (673 mg, 8 mmol) was

1178 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
was purified by recrystallization from methanol to give 6f
(565 mg, 21%) as a yellow solid. 1H NMR (400 MHz, CDCl3):
¤ 5.95 (d, J = 16.7 Hz, 2H), 7.39 (d, J = 16.7 Hz, 2H), 7.50 (s,
4H); 13C NMR (101 MHz, CDCl3): ¤ 98.2, 117.5, 127.9, 135.7,
148.8.25
1389, 1350, 1258, 1202, 1119, 1078, 1028, 833, 814, 775,
756 cm¹1. Anal. Calcd for C29H39NO2Si: C, 75.44; H, 8.51%.
Found: C, 75.53; H, 8.69%.
(Z)-3-(4-N,N-Dimethylaminophenyl)-2-propylhex-2-ene-
nitrile (3fa):
A colorless oil, Rf = 0.61 (hexane-ethyl
Nickel/Lewis Acid-Catalyzed Arylcyanation of Alkynes.
General procedure: In a dry box, to a solution of Ni(cod)2
(2.8-13.7 mg, 10-50 ¯mol) and a ligand (20-100 ¯mol) in
toluene (1.0 mL) placed in a vial, were sequentially added an
aryl cyanide (1.00 mmol), a Lewis acid (40-200 ¯mol), an
alkyne (1.00 mmol), and dodecane (internal standard, 56 mg,
0.33 mmol). The vial was closed, taken out from the dry box,
and heated at the temperature for the time specified in
Tables 1-4. The resulting mixture was filtered through a silica
gel pad and concentrated in vacuo. The residue was purified by
flash silica gel column chromatography to give the correspond-
ing arylcyanation products in yields listed in Tables 1-4.
Regio- and/or stereoisomers were separated by preparative
GPC or HPLC and characterized by spectrometry. The spectra
of (Z)-3aa, -3ba, -3ca, -3da, -3ja, and -3ma agreed well with
those reported previously.1a,1d
Nickel/Lewis Acid-Catalyzed Arylcyanation of Alkynes
Using Dichlorobis(dimethylphenylphosphine)nickel(II) as a
Precatalyst (Scheme 1). In a dry box, to 1a (133 mg, 1.00
mmol) placed in a vial were added a solution of (PhMe2P)2-
NiCl2 (4.1 mg, 10 ¯mol) in toluene (1.0 mL), 2a (110 mg, 1.00
mmol), a 1.0 M solution of AlMe3 in hexane (40 ¯L, 40 ¯mol),
and dodecane (internal standard, 56 mg, 0.33 mmol). The vial
was closed, taken out from the dry box, and heated at 50 °C for
19 h. The resulting mixture was filtered through a silica gel pad
and concentrated in vacuo. The residue was purified by flash
silica gel column chromatography (hexane-ethyl acetate = 8:1)
to give (Z)-3aa (233 mg, 96%).
acetate = 2:1). 1H NMR (400 MHz, CDCl3): ¤ 0.86 (t, J =
7.4 Hz, 3H), 1.01 (t, J = 7.3 Hz, 3H), 1.32 (sext, J = 7.5 Hz,
2H), 1.66 (sext, J = 7.5 Hz, 2H), 2.33 (t, J = 7.7 Hz, 2H), 2.49
(t, J = 7.7 Hz, 2H), 2.98 (s, 6H), 6.70 (d, J = 9.0 Hz, 2H), 7.26
(d, J = 9.0 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.5, 13.8,
21.4, 21.9, 32.7, 35.3, 40.2, 108.9, 111.6, 120.7, 127.3, 128.9,
150.5, 158.8. IR (neat): 2961, 2932, 2872, 2205, 1611, 1524,
1454, 1445, 1360, 1229, 1202, 1167, 947, 820, 733 cm¹1. Anal.
Calcd for C17H24N2: C, 79.64; H, 9.44%. Found: C, 79.64; H,
9.50%.
(Z)-3-(4-N,N-Diphenylaminophenyl)-2-propylhex-2-ene-
nitrile (3ga):
A colorless oil, Rf = 0.24 (hexane-ethyl
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 0.90 (t, J =
7.4 Hz, 3H), 1.01 (t, J = 7.3 Hz, 3H), 1.35 (sext, J = 7.5 Hz,
2H), 1.67 (sext, J = 7.5 Hz, 2H), 2.34 (t, J = 7.6 Hz, 2H), 2.49
(t, J = 7.7 Hz, 2H), 7.00-7.32 (m, 14H); 13C NMR (101 MHz,
CDCl3): ¤ 13.5, 13.9, 21.3, 21.8, 32.7, 35.5, 110.5, 120.1,
122.0, 123.4, 125.0, 128.7, 129.3, 133.1, 147.3, 148.1, 158.3.
IR (neat): 2963, 2932, 2872, 2208, 1591, 1506, 1493, 1327,
1277, 839, 754, 696 cm¹1. HRMS (EI) Calcd for C27H28N2:
M+, 380.2252. Found: m/z 380.2244.
(Z)-3-(4-Bromophenyl)-2-propylhex-2-enenitrile (3ha):
A colorless oil, Rf = 0.53 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.87 (t, J = 7.3 Hz, 3H), 1.01
(t, J = 7.4 Hz, 3H), 1.30 (sext, J = 7.5 Hz, 2H), 1.67 (sext, J =
7.5 Hz, 2H), 2.35 (t, J = 7.6 Hz, 2H), 2.48 (t, J = 7.7 Hz, 2H),
7.18 (d, J = 8.6 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 13.5, 13.8, 21.0, 21.7, 32.4, 35.5, 112.3,
119.3, 122.8, 129.4, 131.7, 138.9, 157.5. IR (neat): 2963,
2932, 2872, 2210, 1587, 1487, 1458, 1393, 1381, 1101, 1072,
1011, 831, 785 cm¹1. HRMS (EI) Calcd for C15H18BrN: M+,
291.0622. Found: m/z 291.0628.
(E)-3-(4-Methoxyphenyl)-2-propylhex-2-enenitrile [(E)-
3aa]: A pale yellow oil, Rf = 0.20 (hexane-ethyl acetate =
1
30:1). H NMR (400 MHz, CDCl3): ¤ 0.85 (t, J = 7.3 Hz, 3H),
0.91 (t, J = 7.4 Hz, 3H), 1.35 (sext, J = 7.4 Hz, 2H), 1.55 (sext,
J = 7.5 Hz, 2H), 2.10 (t, J = 7.6 Hz, 2H), 2.70 (t, J = 7.5 Hz,
2H), 3.84 (s, 3H), 6.91 (dt, J = 8.8, 2.4 Hz, 2H), 7.02 (dt, J =
8.8, 2.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.5, 13.6,
21.2, 21.9, 32.7, 40.5, 55.3, 111.3, 113.7, 119.2, 128.6, 130.3,
158.2, 159.1. IR (neat): 2961, 2934, 2872, 2837, 2207, 1607,
1574, 1510, 1464, 1443, 1412, 1381, 1304, 1288, 1250, 1177,
1109, 1034, 837, 739 cm¹1. HRMS (EI) Calcd for C16H21NO:
M+, 243.1623. Found: m/z 243.1624.
(Z)-3-(4-Chlorophenyl)-2-propylhex-2-enenitrile (3ia):
A
colorless oil, Rf = 0.48 (hexane-ethyl acetate = 5:1).
1H NMR (400 MHz, CDCl3): ¤ 0.87 (t, J = 7.3 Hz, 3H), 1.02
(t, J = 7.4 Hz, 3H), 1.30 (sext, J = 7.5 Hz, 2H), 1.67 (sext, J =
7.5 Hz, 2H), 2.35 (t, J = 7.6 Hz, 2H), 2.49 (t, J = 7.7 Hz, 2H),
7.24 (d, J = 8.6 Hz, 2H), 7.36 (d, J = 8.6 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 13.5, 13.8, 21.0, 21.7, 32.4, 35.6, 112.3,
119.3, 128.7, 129.2, 134.6, 138.5, 157.5. IR (neat): 2963, 2932,
2874, 2210, 1593, 1491, 1458, 1092, 1015, 835 cm¹1. Anal.
Calcd for C15H18ClN: C, 72.71; H, 7.32%. Found: C, 72.97; H,
7.59%.
(Z)-3-(4-{[2-(Tetrahydro-2H-pyran-2-oxymethyl)phenyl]-
dimethylsilyl}phenyl)-2-propylhex-2-enenitrile (3ea):
A
colorless oil, Rf = 0.35 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.60 (s, 3H), 0.61 (s, 3H),
0.87 (t, J = 7.4 Hz, 3H), 1.01 (t, J = 7.4 Hz, 3H), 1.30 (sext,
J = 7.5 Hz, 2H), 1.40-1.83 (m, 8H), 2.35 (t, J = 7.6 Hz, 2H),
2.49 (t, J = 7.8 Hz, 2H), 3.39-3.49 (m, 1H), 3.74-3.84 (m, 1H),
4.39 (d, J = 12.1 Hz, 1H), 4.48 (t, J = 3.5 Hz, 1H), 4.67 (d,
J = 12.1 Hz, 1H), 7.23-7.33 (m, 3H), 7.41 (td, J = 7.5, 1.5 Hz,
1H), 7.47-7.51 (m, 3H), 7.54 (dd, J = 7.5, 1.3 Hz, 1H);
13C NMR (101 MHz, CDCl3): ¤ ¹1.11, ¹0.96, 13.5, 13.8, 19.3,
21.1, 21.7, 25.4, 30.4, 32.5, 35.6, 62.0, 68.8, 97.8, 111.5, 119.6,
126.8, 127.0, 128.5, 129.7, 134.0, 135.5, 135.7, 139.5, 140.6,
144.2, 158.6. IR (neat): 2959, 2872, 2361, 2210, 1458, 1437,
(Z)-3-(2-Methoxyphenyl)-2-propylhex-2-enenitrile (3ka):
A colorless oil, Rf = 0.34 (hexane-ethyl acetate = 7.5:1).
1H NMR (400 MHz, CDCl3): ¤ 0.88 (t, J = 7.4 Hz, 3H), 1.02
(t, J = 7.4 Hz, 3H), 1.30 (sext, J = 7.5 Hz, 2H), 1.67 (sext, J =
7.4 Hz, 2H), 2.36 (t, J = 7.5 Hz, 2H), 2.47 (t, J = 7.8 Hz, 2H),
3.81 (s, 3H), 6.92 (d, J = 8.4 Hz, 1H), 6.96 (td, J = 7.4, 1.0 Hz,
1H), 7.09 (dd, J = 7.5, 1.8 Hz, 1H), 7.31 (ddd, J = 7.8, 7.5,
1.6 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤ 13.4, 14.0, 20.9,
21.7, 31.8, 35.0, 55.5, 111.1, 112.9, 119.4, 120.5, 129.4,
129.68, 129.72, 156.1, 157.0. IR (neat): 2963, 2934, 2872,
2212, 1597, 1578, 1489, 1464, 1435, 1275, 1246, 1178, 1163,

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1179
1124, 1097, 1049, 1026, 799, 752 cm¹1. Anal. Calcd for
C16H21NO: C, 78.97; H, 8.70%. Found: C, 78.86; H, 8.67%.
(Z)-3-(2,6-Dimethylphenyl)-2-propylhex-2-enenitrile (3la):
1148, 1107, 1096, 912, 887, 851, 762, 706, 538 cm¹1. HRMS
(EI) Calcd for C18H19NO2; M+, 281.1416. Found: m/z
281.1418.
A
colorless oil, Rf = 0.53 (hexane-ethyl acetate = 5:1).
(Z)-3-(2-Oxo-2H-chromen-3-yl)-2-propylhex-2-enenitrile
(3qa): A colorless solid, mp 68.6-69.6 °C, Rf = 0.23 (hexane-
ethyl acetate = 7:1). H NMR (400 MHz, CDCl3): ¤ 0.93 (t,
J = 7.3 Hz, 3H), 1.05 (t, J = 7.3 Hz, 3H), 1.40 (sext, J = 7.5
Hz, 2H), 1.70 (sext, J = 7.4 Hz, 2H), 2.39 (t, J = 7.6 Hz, 2H),
2.60 (t, J = 7.8 Hz, 2H), 7.31 (d, J = 7.9 Hz, 1H), 7.36 (d,
J = 8.2 Hz, 1H), 7.51-7.59 (m, 2H), 7.69 (s, 1H); 13C NMR
(101 MHz, CDCl3): ¤ 13.7, 14.0, 21.4, 21.7, 32.0, 33.0, 115.2,
116.5, 118.4, 118.5, 124.6, 127.4, 128.1, 132.1, 142.5, 153.5,
153.7, 159.0. IR (KBr): 3036, 2961, 2932, 2872, 2211, 1713,
1H NMR (400 MHz, CDCl3): ¤ 0.92 (t, J = 7.2 Hz, 3H), 1.05
(t, J = 7.3 Hz, 3H), 1.29-1.42 (m, 2H), 1.70 (sext, J = 7.4 Hz,
2H), 2.22 (s, 6H), 2.35-2.45 (m, 4H), 7.06 (d, J = 7.3 Hz, 2H),
7.13 (dd, J = 8.5, 6.5 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤
13.6, 14.6, 19.8, 20.8, 21.6, 31.6, 36.2, 113.7, 118.7, 127.7,
127.9, 134.6, 139.5, 158.1. IR (neat): 2963, 2932, 2872, 2212,
1464, 1379, 772 cm¹1. Anal. Calcd for C17H23N: C, 84.59; H,
9.60%. Found: C, 84.38; H, 9.71%.
1
(Z)-3-(1-Methylindol-3-yl)-2-propylhex-2-enenitrile (3na):
A pale yellow solid, mp 74.7-75.3 °C, Rf = 0.30 (hexane-ethyl
acetate = 5:1). 1H NMR (400 MHz, CDCl3): ¤ 0.87 (t, J =
7.4 Hz, 3H), 1.05 (t, J = 7.4 Hz, 3H), 1.36 (sext, J = 7.6 Hz,
2H), 1.71 (sext, J = 7.5 Hz, 2H), 2.41 (t, J = 7.6 Hz, 2H), 2.66
(t, J = 7.8 Hz, 2H), 3.81 (s, 3H), 7.17 (t, J = 7.5 Hz, 1H), 7.23-
7.30 (m, 2H), 7.34 (d, J = 8.1 Hz, 1H), 7.58 (d, J = 7.9 Hz,
1H); 13C NMR (101 MHz, CDCl3): ¤ 13.6, 13.9, 21.8, 22.0,
32.4, 33.0, 35.3, 109.4, 109.7, 114.3, 119.9, 120.2, 120.9,
122.0, 126.3, 129.0, 137.0, 152.4. IR (KBr): 2961, 2870, 2201,
1614, 1605, 1537, 1477, 1466, 1385, 1331, 1244, 1134, 1105,
1090, 1015, 845, 741 cm¹1. Anal. Calcd for C18H22N2: C,
81.16; H, 8.32%. Found: C, 81.02; H, 8.47%.
1611, 1570, 1489, 1458, 1381, 1368, 1252, 1225, 1186, 1126,
¹1
1076, 1065, 1036, 984, 972, 926, 910, 800, 764, 741 cm
.
Anal. Calcd for C18H19NO2: C, 76.84; H, 6.81%. Found: C,
76.74; H, 6.75%.
(Z)-3-(4-Chlorophenyl)-2-methylbut-2-enenitrile (3ib):
A colorless oil, Rf = 0.13 (hexane-ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3): ¤ 2.16 (q, J = 1.1 Hz, 3H), 2.41
(q, J = 1.1 Hz, 3H), 7.31 (dt, J = 8.8, 2.2 Hz, 2H), 7.37 (dt,
J = 9.0, 2.2 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 17.7,
20.7, 105.8, 119.9, 128.55, 128.57, 134.5, 139.1, 152.8. IR
(neat): 2997, 2926, 2862, 2211, 1906, 1620, 1593, 1491, 1441,
1398, 1294, 1265, 1186, 1094, 1061, 1013, 968, 947, 833, 725,
638, 613, 602, 579, 521 cm¹1. HRMS (EI) Calcd for
C11H10ClN; M+, 191.0502. Found: m/z 191.0497.
(Z)-3-Ferrocenyl-2-propylhex-2-enenitrile [(Z)-3oa]:
A
red oil, Rf = 0.18 (hexane-ethyl acetate = 20:1). 1H NMR
(400 MHz, CDCl3): ¤ 1.02 (t, J = 7.3 Hz, 6H), 1.54 (sext,
J = 7.7 Hz, 2H), 1.67 (sext, J = 7.5 Hz, 2H), 2.26 (t, J = 7.6
Hz, 2H), 2.48 (distorted t, J = 8.2 Hz, 2H), 4.17 (s, 5H), 4.38 (t,
J = 1.9 Hz, 2H), 4.85 (t, J = 1.9 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 13.7, 14.6, 21.9, 23.8, 33.5, 35.5, 68.7, 69.7, 70.0,
82.4, 104.8, 121.4, 155.5. IR (neat): 3096, 2961, 2932, 2872,
2201, 1591, 1462, 1456, 1412, 1381, 1343, 1302, 1290, 1275,
1236, 1211, 1186, 1107, 1086, 1065, 1042, 1001, 934, 883,
822, 758, 741, 498 cm¹1. Anal. Calcd for C19H23FeN: C, 71.04;
H, 7.22%. Found: C, 71.24; H, 7.12%.
(Z)-3-(4-Chlorophenyl)-2-ethylpent-2-enenitrile (3ic):
A
colorless oil, Rf = 0.13 (hexane-ethyl acetate = 20:1).
1H NMR (400 MHz, CDCl3): ¤ 0.95 (t, J = 7.5 Hz, 3H), 1.24
(t, J = 7.5 Hz, 3H), 2.41 (q, J = 7.5 Hz, 2H), 2.53 (q, J = 7.6
Hz, 2H), 7.25 (dt, J = 8.4, 2.2 Hz, 2H), 7.37 (dt, J = 8.6,
2.2 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 12.6, 13.3, 24.0,
27.0, 113.0, 119.2, 128.6, 129.1, 134.5, 138.1, 158.0. IR (neat):
2974, 2936, 2876, 2211, 1906, 1618, 1593, 1491, 1460, 1397,
1379, 1317, 1269, 1180, 1096, 1053, 1013, 932, 856, 827, 731,
716, 577, 515 cm¹1. Anal. Calcd for C13H14ClN: C, 71.07; H,
6.42%. Found: C, 71.10; H, 6.40%.
(E)-3-Ferrocenyl-2-propylhex-2-enenitrile [(E)-3oa]:
A
red oil, Rf = 0.18 (hexane-ethyl acetate = 20:1). 1H NMR
(400 MHz, CDCl3): ¤ 1.03 (q, J = 7.1 Hz, 6H), 1.67 (sept,
J = 7.8 Hz, 4H), 2.44 (t, J = 7.9 Hz, 2H), 2.73 (distorted t, J =
8.0 Hz, 2H), 4.16 (s, 5H), 4.40 (s, 4H); 13C NMR (101 MHz,
CDCl3): ¤ 13.9, 14.4, 22.0, 24.4, 33.1, 40.1, 69.6, 70.0, 82.0,
108.4, 120.5, 155.8. IR (neat): 3096, 2961, 2930, 2872, 2199,
1589, 1466, 1458, 1412, 1381, 1343, 1327, 1290, 1273, 1261,
1227, 1209, 1119, 1107, 1088, 1061, 1042, 1001, 930, 882,
822, 746, 525 cm¹1. HRMS (EI) Calcd for: C19H23FeN: M+,
321.1180. Found: m/z 321.1182.
(Z)-3-(4-Oxo-4H-chromen-3-yl)-2-propylhex-2-enenitrile
(3pa): A yellow oil, Rf = 0.33 (hexane-ethyl acetate = 7:1).
1H NMR (400 MHz, CDCl3): ¤ 0.92 (t, J = 7.3 Hz, 3H), 1.04 (t,
J = 7.3 Hz, 3H), 1.38 (sext, J = 7.5 Hz, 2H), 1.69 (sext, J =
7.4 Hz, 2H), 2.39 (t, J = 7.6 Hz, 2H), 2.60 (t, J = 7.8 Hz, 2H),
7.44 (t, J = 7.6 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.70 (t, J =
7.9 Hz, 1H), 7.89 (s, 1H), 8.23 (d, J = 7.9 Hz, 1H); 13C NMR
(101 MHz, CDCl3): ¤ 13.6, 14.0, 21.2, 21.7, 32.0, 33.3, 115.3,
118.1, 118.6, 124.1, 124.4, 125.4, 125.9, 133.9, 151.0, 153.5,
156.0, 175.5. IR (neat): 3069, 2963, 2932, 2872, 2212, 1649,
1616, 1572, 1466, 1377, 1350, 1321, 1304, 1296, 1221, 1165,
(Z)-3-(4-Chlorophenyl)-4-trimethylsilyl-2-(trimethylsilyl-
methyl)but-2-enenitrile (3id): A colorless solid, mp 65.9-
66.8 °C, Rf = 0.45 (hexane-ethyl acetate = 10:1). 1H NMR
(400 MHz, CDCl3): ¤ ¹0.10 (s, 9H), 0.17 (s, 9H), 1.77 (s,
2H), 2.03 (s, 2H), 7.27 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 8.4 Hz,
2H); 13C NMR (101 MHz, CDCl3): ¤ ¹0.9, ¹0.7, 22.6, 27.6,
104.8, 120.8, 128.5, 129.3, 134.1, 139.8, 153.0. IR (KBr):
3437, 2955, 2899, 2203, 1906, 1599, 1589, 1489, 1466, 1397,
1304, 1296, 1246, 1202, 1165, 1152, 1134, 1090, 1030, 1013,
903, 839, 789, 775, 766, 739, 725, 698, 675, 652, 629, 608,
521, 503 cm¹1. Anal. Calcd for C17H26ClNSi2: C, 60.76; H,
7.80%. Found: C, 60.54; H, 7.99%.
(Z)-3-(4-Chlorophenyl)-2-isopropylbut-2-enenitrile (3ie):
A colorless oil, Rf = 0.20 (hexane-ethyl acetate = 20:1).
1H NMR (400 MHz, CDCl3): ¤ 1.22 (d, J = 6.8 Hz, 6H), 2.18
(s, 3H), 2.92 (sext, J = 6.8 Hz, 1H), 7.29 (dt, J = 8.8, 2.2 Hz,
2H), 7.36 (dt, J = 8.7, 2.2 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 20.5, 21.2, 29.2, 117.4, 118.9, 128.5, 128.7, 134.4,
139.5, 150.5. IR (neat): 2970, 2932, 2872, 2211, 1904, 1613,
1593, 1491, 1464, 1398, 1389, 1366, 1292, 1263, 1094, 1076,
¹1
1047, 1007, 831, 797, 723, 700, 673, 631, 579, 532, 492 cm
.

1180 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
Anal. Calcd for C13H14ClN: C, 71.07; H, 6.42%. Found: C,
71.36; H, 6.44%.
13.3, 25.8, 55.3, 113.0, 113.8, 119.7, 128.5, 130.6, 130.8,
130.9, 135.2, 138.7, 154.9, 160.1. IR (neat): 2974, 2206, 1607,
1510, 1489, 1460, 1288, 1252, 1175, 1092, 1032, 1015, 908,
833, 824, 731 cm¹1; Calcd for C18H16ClNO: C, 72.60; H,
5.42%. Found: C, 72.40; H, 5.24%.
(Z)-3-(4-Chlorophenyl)-2,4-dimethylpent-2-enenitrile (3¤ie):
A colorless solid, mp 97.8-98.8 °C, Rf = 0.13 (hexane-ethyl
1
acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 0.99 (d, J =
7.0 Hz, 6H), 2.07 (s, 3H), 3.08 (sext, J = 6.9 Hz, 1H), 7.05 (dt,
J = 8.8, 2.2 Hz, 2H), 7.36 (dt, J = 8.8, 2.3 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 16.1, 20.5, 30.7, 107.0, 119.4, 128.4,
129.5, 134.1, 136.2, 162.9. IR (KBr): 3447, 2974, 2932, 2872,
2209, 1908, 1624, 1589, 1489, 1466, 1391, 1364, 1329, 1113,
1103, 1090, 1049, 1015, 963, 878, 845, 814, 731, 723, 567,
548, 521, 469 cm¹1. Anal. Calcd for C13H14ClN: C, 71.07; H,
6.42%. Found: C, 71.07; H, 6.37%.
(Z)-2-tert-Butyl-3-(4-chlorophenyl)but-2-enenitrile (3if):
A colorless oil, Rf = 0.15 (hexane-ethyl acetate = 20:1).
1H NMR (400 MHz, CDCl3): ¤ 1.40 (s, 9H), 2.29 (s, 3H),
7.21 (dt, J = 8.6, 2.2 Hz, 2H), 7.35 (dt, J = 8.4, 2.3 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 23.1, 30.6, 34.2, 118.7, 121.9,
128.55, 128.62, 134.1, 141.9, 154.1. IR (neat): 2970, 2911,
2874, 2207, 1902, 1593, 1489, 1433, 1397, 1368, 1290, 1238,
1206, 1092, 1034, 1015, 831, 783, 687, 577, 532 cm¹1. Anal.
Calcd (as a mixture with 3if and 3¤if) for C14H16ClN: C, 71.94;
H, 6.90%. Found: C, 72.11; H, 6.90%.
(E)-3-(4-Chlorophenyl)-2-trimethylsilylbut-2-enenitrile
[(E)-3ih]: A colorless oil, Rf = 0.14 (hexane-ethyl acetate =
30:1). 1H NMR (400 MHz, CDCl3): ¤ 0.39 (s, 9H), 2.31 (s, 3H),
7.33-7.39 (m, 4H); 13C NMR (101 MHz, CDCl3): ¤ ¹0.2, 24.5,
111.2, 120.1, 128.1, 128.6, 134.9, 140.5, 168.1. IR (neat):
2959, 2195, 1595, 1578, 1556, 1489, 1254, 1103, 1013, 845,
760, 673 cm¹1. Anal. Calcd [as a mixture with (Z)-3ih and 3¤ih]
for C13H16ClNSi: C, 62.50; H, 6.46%. Found: C, 62.75; H,
6.52%.
(Z)-3-(4-Chlorophenyl)-2-trimethylsilylbut-2-enenitrile
[(Z)-3ih]: A colorless oil, Rf = 0.14 (hexane-ethyl acetate =
1
30:1). H NMR (400 MHz, CDCl3): ¤ ¹0.01 (s, 9H), 2.46 (s,
3H), 7.09 (d, J = 8.6 Hz, 2H), 7.35 (d, J = 8.6 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ ¹0.2, 28.2, 113.0, 119.7,
128.1, 128.5, 134.7, 140.3, 169.7. IR (neat): 2959, 2899, 2197,
1599, 1576, 1485, 1435, 1254, 1105, 1090, 1015, 982, 845,
¹1
762, 698, 633, 554 cm
.
(E)-3-(4-Chlorophenyl)-2-methyl-3-(trimethylsilyl)acrylo-
nitrile (3¤ih): A colorless solid, mp 67.2-67.9 °C, Rf = 0.14
(Z)-3-(4-Chlorophenyl)-2,4,4-trimethylpent-2-enenitrile
(3¤if): A colorless solid, mp 76.7-77.5 °C, Rf = 0.15 (hexane-
1
(hexane-ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤
1
ethyl acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 1.18 (s,
0.16 (s, 9H), 2.19 (s, 3H), 6.92 (d, J = 8.5 Hz, 2H), 7.33 (d,
J = 8.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ ¹0.2, 20.5,
118.3, 119.9, 127.7, 128.6, 132.9, 140.9, 161.9. IR (KBr):
9H), 2.21 (s, 3H), 7.00 (dt, J = 8.6, 2.3 Hz, 2H), 7.34 (dt, J =
8.6, 2.2 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 19.1, 30.5,
36.9, 109.6, 120.1, 128.4, 128.6, 133.6, 140.2, 165.7. IR (KBr):
3441, 2969, 2868, 2214, 1591, 1487, 1464, 1397, 1364, 1223,
2957, 2214, 1580, 1487, 1250, 1088, 1013, 908, 843, 800, 760,
¹1
521 cm
.
1198, 1177, 1096, 1047, 1017, 968, 949, 939, 928, 860, 841,
(E)-3-(4-Chlorophenyl)-3-(4-methoxyphenyl)-2-trimethyl-
silylacrylonitrile [(E)-3ii]: A colorless oil, Rf = 0.38
¹1
826, 791, 725, 718, 608, 563, 546, 530, 478 cm
.
1
(Z)-3-(4-Chlorophenyl)-2-(4-methoxyphenyl)pent-2-ene-
nitrile [(Z)-3ig]: A colorless solid, mp 109.8-110.5 °C,
(hexane-ethyl acetate = 5:1). H NMR (400 MHz, CDCl3): ¤
0.10 (s, 9H), 3.85 (s, 3H), 6.88 (d, J = 8.8 Hz, 2H), 7.07 (d, J =
8.8 Hz, 2H), 7.29-7.35 (m, 4H); 13C NMR (101 MHz, CDCl3):
¤ 0.0, 55.4, 111.3, 113.5, 121.0, 128.3, 130.7, 130.8, 133.2,
135.7, 139.6, 160.6, 170.0. IR (neat): 2957, 2899, 2839, 2189,
1607, 1508, 1487, 1304, 1288, 1252, 1175, 1092, 1032, 1015,
845, 802, 760 cm¹1. Anal. Calcd for C19H20ClNOSi: C, 66.74;
H, 5.90%. Found: C, 66.92; H, 5.86%.
1
Rf = 0.34 (hexane-ethyl acetate = 10:1). H NMR (400 MHz,
CDCl3): ¤ 0.93 (t, J = 7.5 Hz, 3H), 2.58 (q, J = 7.5 Hz, 2H),
3.85 (s, 3H), 6.96 (d, J = 8.8 Hz, 2H), 7.30-7.46 (m, 6H);
13C NMR (101 MHz, CDCl3): ¤ 12.8, 27.5, 55.4, 112.1, 114.2,
119.2, 126.4, 128.9, 129.3, 130.1, 135.0, 137.5, 159.8, 159.9.
IR (KBr): 2980, 2963, 2934, 2841, 2206, 1605, 1589, 1570,
1510, 1491, 1464, 1445, 1302, 1283, 1254, 1177, 1105, 1084,
1036, 1011, 845, 829, 689, 515 cm¹1. Anal. Calcd for
C18H16ClNO: C, 72.60; H, 5.42%. Found: C, 72.68; H, 5.67%.
(E)-3-(4-Chlorophenyl)-2-(4-methoxyphenyl)pent-2-ene-
nitrile [(E)-3ig]: A pale yellow oil, Rf = 0.26 (hexane-ethyl
(Z)-3-(4-Chlorophenyl)-3-(4-methoxyphenyl)-2-trimethyl-
silylacrylonitrile [(Z)-3ii]:
A colorless solid, mp 98.7-
99.6 °C, Rf = 0.35 (hexane-ethyl acetate = 5:1). 1H NMR (400
MHz, CDCl3): ¤ 0.07 (s, 9H), 3.83 (s, 3H), 6.87 (d, J = 8.8 Hz,
2H), 7.10 (d, J = 8.5 Hz, 2H), 7.33 (d, J = 8.8 Hz, 2H), 7.36 (d,
J = 8.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 0.0, 55.4,
110.1, 113.5, 121.1, 128.3, 130.7, 131.0, 132.9, 135.3, 139.8,
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 1.06 (t, J =
7.5 Hz, 3H), 2.92 (q, J = 7.5 Hz, 2H), 3.76 (s, 3H), 6.70 (d,
J = 8.8 Hz, 2H), 6.97-7.03 (m, 4H), 7.22 (d, J = 8.4 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 12.6, 32.0, 55.2, 111.4, 113.8,
118.8, 125.7, 128.8, 129.9, 130.7, 134.3, 136.4, 158.2, 159.3.
IR (neat): 2972, 2936, 2212, 1607, 1510, 1489, 1464, 1294,
1254, 1178, 1092, 1034, 1015, 912, 826, 733 cm¹1. HRMS (EI)
Calcd for C18H16ClNO: M+, 297.0920. Found: m/z 297.0932.
(Z)-3-(4-Chlorophenyl)-3-(4-methoxyphenyl)-2-ethylacrylo-
nitrile (3¤ig): A pale yellow oil, Rf = 0.26 (hexane-ethyl
160.8, 169.4. IR (KBr): 2961, 2191, 1601, 1572, 1543, 1508,
¹1
1489, 1306, 1252, 1182, 1167, 1092, 1028, 860, 837 cm
.
Anal. Calcd for C19H20ClNOSi: C, 66.74; H, 5.90%. Found: C,
66.48; H, 5.97%.
Arylcyanation of Norbornadiene. General procedure: In
a dry box, to an aryl cyanide (1.00 mmol) placed in a vial were
sequentially added a solution of Ni(cod)2 (2.8 mg, 10 ¯mol)
and Me2P(CH2)2PMe2 (1.5 mg, 10 ¯mol) in toluene (0.67 mL),
a 1.04 M solution of AlMe2Cl in hexane (39 ¯L, 40 ¯mol),
norbornadiene (138 mg, 1.50 mmol), and dodecane (internal
standard, 85 mg, 0.50 mmol). The vial was closed, taken out
from the dry box, and heated at 80 °C for the time specified in
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 1.24 (t, J =
7.4 Hz, 3H), 2.42 (q, J = 7.5 Hz, 2H), 3.83 (s, 3H), 6.90 (d,
J = 8.4 Hz, 2H), 7.03 (d, J = 9.0 Hz, 2H), 7.27 (d, J = 8.4 Hz,
2H), 7.33 (d, J = 8.4 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1181
Table 5. The resulting mixture was filtered through a silica gel
pad and concentrated in vacuo. The residue was purified by
flash silica gel column chromatography to give the correspond-
ing arylcyanation products in yields listed in Table 5.
(dd, J = 9.1, 1.9 Hz, 1H), 3.02 (dd, J = 9.1, 1.4 Hz, 1H), 3.17
(d, J = 1.5 Hz, 1H), 3.35 (s, 1H), 6.20 (dd, J = 5.6, 3.0 Hz,
1H), 6.43 (dd, J = 5.7, 3.3 Hz, 1H), 7.13 (dt, J = 8.2, 2.1 Hz,
2H), 7.49 (dt, J = 8.6, 2.3 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 36.4, 46.16, 46.20, 46.7, 48.2, 120.9, 121.1, 129.7,
131.8, 135.5, 139.0, 140.5. IR (KBr): 2978, 2924, 2236, 1489,
1404, 1327, 1072, 1009, 835, 768, 716 cm¹1. Anal. Calcd for
C14H12BrN: C, 61.33; H, 4.41%. Found: C, 61.53; H, 4.62%.
(5R*,6S*)-6-(4-Chlorophenyl)-5-cyanobicyclo[2.2.1]hept-
2-ene (5i): A colorless solid, mp 147.4-148.3 °C, Rf = 0.34
(5R*,6S*)-5-Cyano-6-(4-methoxyphenyl)bicyclo[2.2.1]-
hept-2-ene (5a):
A colorless solid, mp 67.3-68.1 °C,
Rf = 0.19 (hexane-ethyl acetate = 7:1). 1H NMR (400 MHz,
CDCl3): ¤ 1.78 (dt, J = 9.4, 1.8 Hz, 1H), 2.11 (d, J = 9.3 Hz,
1H), 2.78 (dd, J = 9.1, 1.8 Hz, 1H), 3.03 (dd, J = 9.0, 1.5 Hz,
1H), 3.16 (d, J = 1.3 Hz, 1H), 3.33 (s, 1H), 3.80 (s, 3H), 6.18
(dd, J = 5.8, 3.0 Hz, 1H), 6.43 (dd, J = 5.7, 3.3 Hz, 1H),
6.90 (dt, J = 8.8, 2.6 Hz, 2H), 7.17 (dt, J = 8.4, 1.7 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 36.5, 46.2, 46.47, 46.53, 48.2,
55.2, 114.0, 121.3, 129.0, 131.8, 135.3, 140.8, 158.5. IR (KBr):
2976, 2234, 1611, 1512, 1460, 1250, 1182, 1034, 835, 764,
729, 692 cm¹1. Anal. Calcd for C15H15NO: C, 79.97; H, 6.71%.
Found: C, 79.92; H, 6.74%.
1
(hexane-ethyl acetate = 5:1). H NMR (400 MHz, CDCl3): ¤
1.82 (dt, J = 9.3, 1.8 Hz, 1H), 2.08 (d, J = 9.5 Hz, 1H), 2.83
(dd, J = 9.1, 1.8 Hz, 1H), 3.04 (dd, J = 9.1, 1.4 Hz, 1H), 3.19
(d, J = 1.5 Hz, 1H), 3.36 (s, 1H), 6.20 (dd, J = 5.7, 2.9 Hz,
1H), 6.44 (dd, J = 5.6, 3.2 Hz, 1H), 7.19 (dt, J = 8.4, 2.0 Hz,
2H), 7.34 (dt, J = 8.4, 2.3 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 36.4, 46.15, 46.24, 46.6, 48.2, 120.8, 129.4, 132.9,
135.5, 138.5, 140.5. IR (KBr): 2978, 2924, 2238, 1493, 1408,
1327, 1088, 1013, 839, 768, 719, 671 cm¹1. Anal. Calcd for
C14H12ClN: C, 73.20; H, 5.27%. Found: C, 73.11; H, 5.34%.
(5R*,6S*)-5-Cyano-6-(2-methoxyphenyl)bicyclo[2.2.1]-
(5R*,6S*)-5-Cyano-6-(4-methylphenyl)bicyclo[2.2.1]hept-
2-ene (5b): A colorless solid, mp 81.4-84.0 °C, Rf = 0.20
1
(hexane-ethyl acetate = 10:1). H NMR (400 MHz, CDCl3): ¤
1.79 (dt, J = 9.3, 1.8 Hz, 1H), 2.11 (d, J = 9.3 Hz, 1H), 2.34 (s,
3H), 2.81 (dd, J = 9.1, 1.9 Hz, 1H), 3.04 (dd, J = 9.0, 1.5 Hz,
1H), 3.19 (d, J = 1.5 Hz, 1H), 3.33 (d, J = 0.6 Hz, 1H), 6.18
(dd, J = 5.7, 2.9 Hz, 1H), 6.43 (dd, J = 5.7, 3.1 Hz, 1H), 7.14
(d, J = 8.2 Hz, 2H), 7.17 (d, J = 8.2 Hz, 2H); 13C NMR (101
MHz, CDCl3): ¤ 21.1, 36.5, 46.2, 46.3, 46.8, 48.2, 121.3,
hept-2-ene (5k):
A colorless solid, mp 98.0-98.5 °C,
Rf = 0.38 (hexane-ethyl acetate = 5:1). 1H NMR (400 MHz,
CDCl3): ¤ 1.74 (dt, J = 9.2, 1.9 Hz, 1H), 1.97 (d, J = 9.2 Hz,
1H), 2.91 (dd, J = 8.8, 2.0 Hz, 1H), 3.15 (dd, J = 8.7, 1.7 Hz,
1H), 3.26-3.31 (m, 2H), 3.85 (s, 3H), 6.20 (dd, J = 5.7, 2.9 Hz,
1H), 6.39 (dd, J = 5.7, 3.1 Hz, 1H), 6.90 (dd, J = 8.2, 0.9 Hz,
1H), 6.99 (td, J = 7.5, 1.0 Hz, 1H), 7.23 (d, J = 7.7 Hz, 1H),
7.28 (td, J = 7.8, 1.5 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤
35.7, 41.5, 44.0, 45.8, 48.0, 55.2, 110.0, 120.5, 121.5, 126.0,
128.1, 129.0, 135.7, 139.7, 157.8. IR (KBr): 2976, 2236, 1601,
1587, 1489, 1337, 1246, 1101, 1051, 1032, 750, 719, 706
cm¹1. Anal. Calcd for C15H15NO: C, 79.97; H, 6.71%. Found:
C, 80.23; H, 6.66%.
127.9, 129.4, 135.3, 136.6, 136.8, 140.7. IR (KBr): 2978, 2922,
¹1
2234, 1514, 1456, 1327, 1263, 827, 758, 727, 696, 505 cm
.
Anal. Calcd for C15H15N: C, 86.08; H, 7.22%. Found: C,
86.27; H, 7.35%.
(5R*,6S*)-5-Cyano-6-phenylbicyclo[2.2.1]hept-2-ene (5c):
A colorless solid, mp 94.3-94.7 °C, Rf = 0.21 (hexane-ethyl
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 1.80 (dt, J =
9.3, 1.8 Hz, 1H), 2.12 (d, J = 9.3 Hz, 1H), 2.83 (dd, J = 9.1,
1.9 Hz, 1H), 3.08 (dd, J = 9.1, 1.5 Hz, 1H), 3.22 (d, J = 1.3 Hz,
1H), 3.34 (s, 1H), 6.19 (dd, J = 5.7, 2.9 Hz, 1H), 6.44 (dd,
J = 5.7, 3.3 Hz, 1H), 7.24-7.30 (m, 3H), 7.34-7.40 (m, 2H);
13C NMR (101 MHz, CDCl3): ¤ 36.5, 46.2, 46.3, 47.2, 48.2,
121.1, 127.1, 128.0, 128.7, 135.3, 139.9, 140.7. IR (KBr):
2996, 2951, 2230, 1451, 1327, 1263, 1098, 1076, 799, 723,
712, 700 cm¹1. Anal. Calcd for C14H13N: C, 86.12; H, 6.71%.
Found: C, 86.09; H, 6.65%.
Nickel/BPh3-Catalyzed Alkenylcyanation of Alkynes.
General procedure: In a dry box, to a solution of Ni(cod)2
(20-50 ¯mol) and ligand (40-100 ¯mol) in toluene (1.0 mL)
placed in a vial were added an alkenyl cyanide (1.00 mmol),
BPh3 (80-200 ¯mol), an alkyne (1.20-2.0 mmol), and dodecane
(internal standard, 85 mg, 0.50 mmol). The vial was closed,
taken out from the dry box, and heated at 80 °C for the time
specified in Table 6. The resulting mixture was filtered through
a silica gel pad and concentrated in vacuo. The residue was
purified by flash silica gel column chromatography to give the
corresponding alkenylcyanation products in yields listed in
Table 6.
(2Z,4E)-5-Phenyl-2,3-dipropylpenta-2,4-dienenitrile (7aa):
A pale yellow oil, Rf = 0.13 (hexane-ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3): ¤ 1.00 (t, J = 7.4 Hz, 3H), 1.02 (t,
J = 7.5 Hz, 3H), 1.53 (sext, J = 7.6 Hz, 2H), 1.66 (sext, J =
7.5 Hz, 2H), 2.33 (t, J = 7.6 Hz, 2H), 2.46 (t, J = 8.0 Hz,
2H), 6.84 (d, J = 16.1 Hz, 1H), 7.26-7.40 (m, 4H), 7.52 (d,
J = 7.1 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.6, 14.3,
21.8, 22.6, 29.9, 32.2, 112.4, 119.1, 127.0, 127.1, 128.7, 128.8,
133.5, 136.2, 153.1. IR (neat): 2963, 2934, 2874, 2203, 1692,
1450, 962, 754, 692 cm¹1. Anal. Calcd for C17H21N: C, 85.30;
H, 8.84%. Found: C, 85.54; H, 8.78%.
(5R*,6S*)-5-Cyano-6-(4-N,N-dimethylaminophenyl)bi-
cyclo[2.2.1]hept-2-ene (5f):
A yellow solid, mp 130.5-
131.1 °C, Rf = 0.28 (hexane-ethyl acetate = 5:1). 1H NMR
(400 MHz, CDCl3): ¤ 1.77 (dt, J = 9.4, 1.9 Hz, 1H), 2.12 (d,
J = 9.3 Hz, 1H), 2.78 (dd, J = 9.0, 1.8 Hz, 1H), 2.94 (s, 6H),
2.99 (dd, J = 9.0, 1.5 Hz, 1H), 3.14 (d, J = 1.5 Hz, 1H), 3.32
(s, 1H), 6.16 (dd, J = 5.6, 3.0 Hz, 1H), 6.42 (dd, J = 5.7,
3.1 Hz, 1H), 6.74 (d, J = 7.9 Hz, 2H), 7.13 (d, J = 8.6 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 36.5, 40.5, 46.4, 46.6, 48.1,
112.7, 121.5, 127.3, 128.6, 135.1, 140.8, 149.4. IR (KBr):
2918, 2236, 1614, 1522, 1447, 1354, 1234, 1200, 1167, 1063,
951, 824, 729, 689 cm¹1. Anal. Calcd for C16H18N2: C, 80.63;
H, 7.61%. Found: C, 80.38; H, 7.59%.
(5R*,6S*)-6-(4-Bromophenyl)-5-cyanobicyclo[2.2.1]hept-
2-ene (5h): A colorless solid, mp 141.8-142.1 °C, Rf = 0.30
1
(hexane-ethyl acetate = 5:1). H NMR (400 MHz, CDCl3): ¤
(2Z,4Z)-2,3-Dipropylhepta-2,4-dienenitrile [(Z)-7ba]:
A
1.80 (dt, J = 9.5, 1.8 Hz, 1H), 2.06 (d, J = 9.7 Hz, 1H), 2.82
colorless oil, Rf = 0.15 (hexane-ethyl acetate = 30:1).

1182 Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010)
Aryl- and Alkenylcyanation
1H NMR (400 MHz, CDCl3): ¤ 0.92 (t, J = 7.3 Hz, 3H), 0.98 (t,
J = 7.3 Hz, 3H), 1.03 (t, J = 7.5 Hz, 3H), 1.42 (sext, J =
7.5 Hz, 2H), 1.62 (sext, J = 7.4 Hz, 2H), 2.13 (qdd, J = 7.5,
7.3, 1.8 Hz, 2H), 2.20 (t, J = 7.7 Hz, 2H), 2.25 (t, J = 7.6 Hz,
2H), 5.66 (dt, J = 11.7, 7.3 Hz, 1H), 5.89 (d, J = 11.7 Hz, 1H);
13C NMR (101 MHz, CDCl3): ¤ 13.7, 13.9, 14.1, 21.3, 21.9,
22.9, 31.8, 34.4, 111.5, 119.5, 126.8, 137.6, 154.7. IR (neat):
2964, 2934, 2874, 2208, 1458, 1379 cm¹1. Anal. Calcd for
C13H21N: C, 81.61; H, 11.06%. Found: C, 81.77; H, 10.82%.
127.0, 128.2, 128.56, 128.61, 133.8, 136.0, 146.6. IR (neat):
3080, 3059, 3040, 2969, 2930, 2872, 2201, 1622, 1599, 1580,
1493, 1464, 1449, 1387, 1366, 1317, 1213, 1180, 1157, 1105,
1074, 1045, 1024, 999, 961, 914, 870, 853, 750, 692, 581,
525 cm¹1. Anal. Calcd for C15H17N: C, 85.26; H, 8.11%.
Found (as a mixture with 7ae and 7¤ae): C, 84.98; H, 8.18%.
(2Z,4E)-3-Isopropyl-2-methyl-5-phenylpenta-2,4-diene-
nitrile (7¤ae): A pale yellow oil, Rf = 0.30 (hexane-ethyl
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 1.21 (d, J =
(2Z,4E)-2,3-Dipropylhepta-2,4-dienenitrile [(E)-7ba]:
A
7.0 Hz, 6H), 2.06 (s, 3H), 3.05 (sept, J = 7.0 Hz, 1H), 6.93
(d, J = 16.3 Hz, 1H), 7.02 (d, J = 16.3 Hz, 1H), 7.29 (t, J =
7.2 Hz, 1H), 7.32-7.38 (m, 2H), 7.48 (d, J = 7.0 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 17.1, 20.7, 29.6, 103.9, 120.5,
124.5, 126.8, 128.4, 128.6, 135.1, 136.2, 159.5. IR (neat):
3080, 3057, 3026, 2967, 2932, 2874, 2203, 1632, 1620, 1599,
1576, 1495, 1462, 1449, 1387, 1366, 1329, 1304, 1273, 1236,
colorless oil, Rf = 0.15 (hexane-ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3): ¤ 0.966 (t, J = 7.4 Hz, 3H),
0.972 (t, J = 7.3 Hz, 3H), 1.07 (t, J = 7.4 Hz, 3H), 1.44 (sext,
J = 7.6 Hz, 2H), 1.61 (sext, J = 7.5 Hz, 2H), 2.19-2.28 (m,
4H), 2.32 (t, J = 8.0 Hz, 2H), 6.07 (dt, J = 15.6, 6.7 Hz, 1H),
6.60 (dt, J = 15.6, 1.5 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤
13.5, 13.8, 14.4, 21.9, 22.7, 26.4, 30.1, 32.0, 109.8, 119.2,
128.0, 138.3, 153.4. IR (neat): 2964, 2934, 2874, 2205, 1638,
1570, 1462, 1381, 1088, 966 cm¹1. HRMS (EI) Calcd for
C13H21N: M+, 191.1674. Found: m/z 191.1675.
(Z)-4-Cyclohexylidene-2,3-dipropylbut-2-enenitrile (7ca):
A pale yellow oil, Rf = 0.28 (hexane-ethyl acetate = 40:1).
1H NMR (400 MHz, CDCl3): ¤ 0.90 (t, J = 7.4 Hz, 3H), 0.96
(t, J = 7.4 Hz, 3H), 1.40 (sext, J = 7.5 Hz, 2H), 1.52-1.65 (m,
8H), 2.10-2.27 (m, 8H), 5.62 (s, 1H); 13C NMR (101 MHz,
CDCl3): ¤ 13.5, 14.0, 21.1, 21.8, 26.4, 27.1, 28.3, 30.6, 31.7,
34.7, 37.1, 111.1, 119.9, 121.0, 146.6, 155.3. IR (neat): 2961,
2932, 2872, 2856, 2208, 1647, 1611, 1448, 1379, 1342, 1234,
1109, 1088, 833, 735 cm¹1. Anal. Calcd for C16H25N: C, 83.06;
H, 10.89%. Found: C, 82.85; H, 10.71%.
1209, 1180, 1157, 1146, 1103, 1067, 1032, 966, 756, 727, 692,
¹1
542, 471 cm
.
(2E,4E)-2-Methyl-5-phenyl-3-(trimethylsilyl)penta-2,4-
dienenitrile (7¤ah): A pale yellow oil, Rf = 0.25 (hexane-
1
ethyl acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 0.33 (s,
9H), 2.15 (s, 3H), 6.70 (d, J = 16.1 Hz, 1H), 7.02 (d, J = 16.3
Hz, 1H), 7.24-7.30 (m, 1H), 7.34 (t, J = 7.5 Hz, 2H), 7.45 (d,
J = 7.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 1.0, 21.2,
110.7, 119.5, 126.9, 128.4, 128.9, 130.3, 134.4, 136.8, 157.7.
IR (neat): 3080, 3059, 3026, 2955, 2899, 2203, 1616, 1599,
1576, 1539, 1491, 1449, 1410, 1379, 1323, 1254, 1209,
1180, 1157, 1111, 1072, 1013, 963, 909, 885, 843, 804, 746,
692, 629, 509 cm¹1. HRMS (EI) Calcd for C15H19NSi: M+,
241.1287. Found: m/z 241.1291. The regiochemistry was
assigned based on HMBC experiments.
(2Z,4E)-2-Methyl-3,5-diphenylpenta-2,4-dienenitrile (7¤aj):
A pale yellow oil, Rf = 0.25 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 1.84 (s, 3H), 6.26 (d, J = 15.7
Hz, 1H), 7.14 (d, J = 8.1 Hz, 2H), 7.27-7.34 (m, 3H), 7.39-
7.49 (m, 5H), 7.58 (d, J = 15.7 Hz, 1H); 13C NMR (101 MHz,
CDCl3): ¤ 18.1, 106.6, 119.3, 127.0, 127.7, 128.2, 128.5,
128.7, 135.3, 135.7, 137.9, 154.6. IR (neat): 3080, 3057, 3032,
2918, 2857, 2207, 1613, 1579, 1576, 1491, 1449, 1379, 1329,
1302, 1265, 1204, 1179, 1157, 1101, 1072, 1017, 1001, 964,
910, 773, 756, 723, 692, 552, 536 cm¹1. HRMS (EI) Calcd for
C18H15N: M+, 245.1204. Found: m/z 245.1203. The regio-
chemistry was assigned based on HMBC experiments.
Nickel/BPh3-Catalyzed Addition Reaction of 1,4-Bis(¢-
cyanovinyl)benzene (6f) across 2a (eq 2). In a dry box, to 6f
(180 mg, 1.00 mmol) placed in a vial were sequentially added a
solution of Ni(cod)2 (11.0 mg, 40 ¯mol) and PMe3 (6.1 mg,
80 ¯mol) in toluene (1.0 mL), BPh3 (38 mg, 160 ¯mol), 2a
(331 mg, 3.0 mmol). The vial was closed, taken out from the
dry box, and heated at 80 °C for 44 h. The resulting mixture
was filtered through a silica gel pad and concentrated in vacuo.
The residue was purified by flash silica gel column chroma-
tography (hexane-toluene = 2:3 to toluene, then CH2Cl2) to
give 7fa (335 mg, 84%) as a yellow solid, mp 147.2-148.2 °C,
Rf = 0.20 (hexane-toluene = 1:2). 1H NMR (400 MHz,
CDCl3): ¤ 1.01 (t, J = 7.4 Hz, 6H), 1.03 (t, J = 7.4 Hz, 6H),
1.54 (sext, J = 7.6 Hz, 4H), 1.67 (sext, J = 7.5 Hz, 4H), 2.34 (t,
J = 7.6 Hz, 4H), 2.46 (distorted t, J = 8.0 Hz, 4H), 6.82 (d,
J = 15.9 Hz, 2H), 7.37 (d, J = 15.9 Hz, 2H), 7.50 (s, 4H);
(Z)-5,5-Diphenyl-2,3-dipropylpenta-2,4-dienenitrile (7da):
A colorless solid, mp 58.1-58.7 °C, Rf = 0.25 (hexane-ethyl
1
acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 0.74 (t, J =
7.4 Hz, 3H), 0.91 (t, J = 7.3 Hz, 3H), 1.32 (sext, J = 7.5 Hz,
2H), 1.54 (sext, J = 7.5 Hz, 2H), 1.89 (t, J = 7.8 Hz, 2H), 2.20
(t, J = 7.5 Hz, 2H), 6.83 (s, 1H), 7.16-7.40 (m, 10H); 13C NMR
(101 MHz, CDCl3): ¤ 13.5, 13.9, 21.7, 22.0, 31.8, 32.8, 113.6,
119.5, 126.6, 128.0, 128.2, 129.9, 139.8, 142.2, 146.8, 155.6.
IR (KBr): 2963, 2932, 2870, 2203, 1599, 1493, 1445, 1375,
870, 779, 762, 696 cm¹1. Anal. Calcd for C23H25N: C, 87.57;
H, 7.99%. Found: C, 87.46; H, 8.04%.
(2Z,4Z)-4-Cyano-5-phenyl-2,3-dipropylpenta-2,4-diene-
nitrile (7ea): A pale yellow oil, Rf = 0.10 (hexane-ethyl
1
acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 0.98 (t, J =
7.4 Hz, 3H), 1.03 (t, J = 7.3 Hz, 3H), 1.53 (sext, J = 7.5 Hz,
2H), 1.69 (sext, J = 7.5 Hz, 2H), 2.36 (t, J = 7.7 Hz, 2H), 2.49
(t, J = 7.8 Hz, 2H), 7.36 (s, 1H), 7.44-7.49 (m, 3H), 7.81-7.89
(m, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.7, 13.9, 21.4, 21.7,
32.8, 33.0, 109.6, 114.7, 116.3, 118.1, 128.9, 129.4, 131.3,
132.4, 148.2, 152.0. IR (neat): 2964, 2933, 2874, 2212, 1605,
1574, 1448, 1381, 1092, 935, 758, 691 cm¹1. Anal. Calcd for
C18H20N2: C, 81.78; H, 7.63%. Found: C, 81.83; H, 7.66%.
(2Z,4E)-2-Isopropyl-3-methyl-5-phenylpenta-2,4-diene-
nitrile (7ae): A pale yellow oil, Rf = 0.30 (hexane-ethyl
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 1.20 (d, J =
6.8 Hz, 6H), 2.09 (s, 3H), 2.94 (sept, J = 6.8 Hz, 1H), 6.86 (d,
J = 15.9 Hz, 1H), 7.30 (t, J = 7.2 Hz, 1H), 7.36 (t, J = 7.3 Hz,
2H), 7.42 (d, J = 15.9 Hz, 1H), 7.51 (d, J = 7.1 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 14.1, 21.5, 28.7, 117.3, 119.3,

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 10 (2010) 1183
13C NMR (101 MHz, CDCl3): ¤ 13.8, 14.5, 21.9, 22.7, 30.0,
32.3, 112.6, 119.0, 127.3, 127.4, 132.7, 136.5, 152.9. IR (KBr):
3428, 3040, 2959, 2934, 2872, 2199, 1614, 1574, 1516, 1479,
1464, 1454, 1433, 1422, 1379, 1335, 1285, 1209, 1161, 1115,
1086, 1071, 968, 903, 880, 822, 739, 658, 552, 534 cm¹1. Anal.
Calcd for C28H36N2: C, 83.95; H, 9.06%. Found: C, 83.99; H,
9.06%.
Org. Lett. 2005, 7, 2639. b) Y. Nishihara, Y. Inoue, S. Izawa, M.
Miyasaka, K. Tanemura, K. Nakajima, K. Takagi, Tetrahedron
2006, 62, 9872. c) Y. Nishihara, M. Miyasaka, Y. Inoue, T.
Yamaguchi, M. Kojima, K. Takagi, Organometallics 2007, 26,
4054.
3
Palladium-catalyzed intramolecular cyanocarbamoylation
of unsaturated bonds, see: a) Y. Kobayashi, H. Kamisaki, R.
Yanada, Y. Takemoto, Org. Lett. 2006, 8, 2711. b) Y. Kobayashi,
H. Kamisaki, H. Takeda, Y. Yasui, R. Yanada, Y. Takemoto,
Tetrahedron 2007, 63, 2978. c) Y. Yasui, H. Kamisaki, Y.
Takemoto, Org. Lett. 2008, 10, 3303. d) Y. Yasui, T. Kinugawa,
Y. Takemoto, Chem. Commun. 2009, 4275. e) V. J. Reddy, C. J.
Douglas, Org. Lett. 2010, 12, 952. f) Y. Yasui, H. Kamisaki, T.
Ishida, Y. Takemoto, Tetrahedron 2010, 66, 1980.
Conversion of 7aa to 1-Phenyl-3,4-dipropylpyridine (8)
(eq 3): To a solution of 7aa (72 mg, 0.30 mmol) in toluene
(15 mL) was added a 1.5 M solution of DIBAL-H in toluene
(0.40 mL, 0.60 mmol) at 0 °C, and the resulting mixture was
stirred at the same temperature for 15 min. The reaction was
quenched with MeOH (0.150 mL) at 0 °C and heated at 100 °C
for 5 h in the open air. To the resulting mixture was added a
slurry of SiO2 (3.0 g) in water (0.90 mL), and the whole was
stirred at rt for 45 min. Anhydrous MgSO4 (0.50 g) and K2CO3
(0.50 g) were added, and the resulting mixture was further
stirred for 90 min, filtered through a Celite pad, and concen-
trated in vacuo. The residue was purified by flash chromatog-
raphy on silica gel (hexane-ethyl acetate = 35:1) to give 8
(44 mg, 61%) as a pale yellow oil, Rf = 0.43 (hexane-ethyl
acetate = 7:1). 1H NMR (400 MHz, CDCl3): ¤ 1.01 (t, J =
7.2 Hz, 3H), 1.02 (t, J = 7.3 Hz, 3H), 1.58-1.74 (m, 4H), 2.59-
2.68 (m, 4H), 7.34-7.41 (m, 1H), 7.42-7.48 (m, 2H), 7.50 (s,
1H), 7.93-7.99 (m, 2H), 8.43 (s, 1H); 13C NMR (101 MHz,
CDCl3): ¤ 14.07, 14.11, 23.5, 24.1, 31.8, 34.1, 120.7, 126.7,
128.4, 128.6, 134.5, 139.6, 149.8, 150.3, 155.0. IR (neat):
2959, 2932, 2870, 1597, 1477, 1377, 777, 694 cm¹1. Anal.
Calcd for C17H21N: C, 85.30; H, 8.84%. Found: C, 85.51; H,
9.12%.
4
Y.-y. Ohnishi, Y. Nakao, H. Sato, Y. Nakao, T. Hiyama, S.
Sakaki, Organometallics 2009, 28, 2583.
Similar ©2-arene nickel intermediate is also suggested in the
5
Ph-CN ·-bond activation by Ni(dmpe), see: T. A. Ateşin, T. Li, S.
Lachaize, J. J. García, W. D. Jones, Organometallics 2008, 27,
3811.
6
a) K. Starowieyski, S. Pasynkiewicz, M. Boleslawski,
J. Organomet. Chem. 1967, 10, 393. b) C. A. Tolman, W. C.
Seidel, J. D. Druliner, P. J. Domaille, Organometallics 1984, 3, 33.
c) N. M. Brunkan, D. M. Brestensky, W. D. Jones, J. Am. Chem.
Soc. 2004, 126, 3627.
7
J. Huang, C. M. Haar, S. P. Nolan, J. E. Marcone, K. G.
Moloy, Organometallics 1999, 18, 297.
For preliminary communication, see: Y. Nakao, A. Yada, S.
Ebata, T. Hiyama, J. Am. Chem. Soc. 2007, 129, 2428.
Nickel/Lewis acid-catalyzed carbocyanation reaction using
8
9
other nitriles, see: a) Y. Nakao, Y. Hirata, M. Tanaka, T. Hiyama,
Angew. Chem., Int. Ed. 2008, 47, 385. b) M. P. Watson, E. N.
Jacobsen, J. Am. Chem. Soc. 2008, 130, 12594. c) Y. Nakao, S.
Ebata, A. Yada, T. Hiyama, M. Ikawa, S. Ogoshi, J. Am. Chem.
Soc. 2008, 130, 12874. d) A. Yada, T. Yukawa, Y. Nakao, T.
Hiyama, Chem. Commun. 2009, 3931. e) A. Yada, T. Yukawa, H.
Idei, Y. Nakao, T. Hiyama, Bull. Chem. Soc. Jpn. 2010, 83, 619.
Also see: Refs. 1h and 1i.
10 Y. Nakao, H. Imanaka, A. K. Sahoo, A. Yada, T. Hiyama,
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This work has been supported financially by a Grant-in-Aid
for Creative Scientific Research, Scientific Research (S), Young
Scientists (A), and Priority Areas “Molecular Theory for Real
Systems” from MEXT and by General Sekiyu Research &
Development Encouragement & Assistance Foundation. AY
acknowledges the JSPS for a predoctoral fellowship.
Supporting Information
1
Copies of H and 13C NMR spectra of compounds (E)-3aa,
12 M. Suginome, A. Yamamoto, M. Murakami, Angew.
Chem., Int. Ed. 2005, 44, 2380.
13 Carbocyanation across norbornadiene, see: Refs. 1e, 1h,
and 2.
3ga, 3ha, (E)-3oa, 3pa, 3ib, (E)-3ig, (E)-7ba, 7¤ah, and 7¤aj.
This material is available free of charge on the web at http://
www.csj.jp/journals/bcsj/.
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