Nickel/Lewis acid-catalyzed carbocyanation of alkynes using acetonitrile and substituted acetonitriles

Article abstract of DOI:10.1246/bcsj.20100023

Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction of butyronitrile gives significant amounts of hydrocyanation products due possibly to β hydride elimination of a propylnickel intermediate. The reaction of optically active α phenylpropionitrile suggests a reaction mechanism that involves oxidative addition of a CCN bond with retention of its absolute configuration.

Full text of DOI:10.1246/bcsj.20100023

© 2010 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 83, No. 6, 619–634 (2010)
619
BCSJ Award Article
Nickel/Lewis Acid-Catalyzed Carbocyanation of Alkynes
Using Acetonitrile and Substituted Acetonitriles
Akira Yada, Tomoya Yukawa, Hiroaki Idei, Yoshiaki Nakao,* and Tamejiro Hiyama*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510
Received January 26, 2010; E-mail: yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and
substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes
is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction
of butyronitrile gives significant amounts of hydrocyanation products due possibly to ¢-hydride elimination of a
propylnickel intermediate. The reaction of optically active ¡-phenylpropionitrile suggests a reaction mechanism that
involves oxidative addition of a C-CN bond with retention of its absolute configuration.
Stereoselective construction of polysubstituted alkenes has
been a major subject in organic synthesis.1 To this end, we2 and
others3 have demonstrated carbocyanation reaction4 of alkynes
catalyzed by nickel or palladium as a new entry to stereo-
chemically well-defined and atom economical protocols for
the synthesis of tri- or disubstituted acrylonitriles, versatile
synthetic intermediates for polysubstituted alkenes. We have
recently disclosed that a Lewis acid (LA) cocatalyst signifi-
cantly improves the efficiency of the nickel-catalyzed carbo-
cyanation of unsaturated bonds, and allows a wide variety of
nitriles including aryl,2d alkenyl,2d alkynyl,2e,2f and allyl2g
cyanides to participate in the reaction. We further anticipated
carbocyanation using alkyl cyanides might be feasible under
similar dual catalysis, because some alkyl cyanides were
reported to undergo oxidative addition to nickel(0) through
the activation of C(sp3)-CN ·-bonds.5 In this paper, we
report a full scope of the carbocyanation reaction of alkynes
with acetonitrile under nickel/AlMe3 dual catalysis. The
reactions of propionitrile and butyronitrile with alkynes are
also described briefly. Also demonstrated is the addition
reaction of substituted acetonitriles such as aryl- and silyl-
acetonitriles as well as protected amino- and hydroxyaceto-
nitriles to give regio- and stereoselectively a wide variety
of tri- and disubstituted acrylonitriles having allylic functional
groups.6
screening several combinations of catalysts and conditions, we
found that the reaction of 1a (10 mmol) with 2a (10 mmol)
proceeded in the presence of Ni(cod)2 (5 mol %), PPh2(t-Bu)
(10 mol %), and AlMe3 (20 mol %) in toluene at 80 °C to give
the corresponding cis-methylcyanation product 3aa in 71%
yield after 4 h (Entry 1 of Table 1).2d Exclusive cis-addition of
1a was unambiguously confirmed by NOE experiments. In the
absence of the LA cocatalyst, the methylcyanation product was
not observed in any detectable amount. Use of CH3CN-d3 as
a nitrile substrate gave 3aa-d3 of 99% deuterium content,
suggesting that the methyl group in 3aa was fully derived from
acetonitrile and definitely not from AlMe3 (Entry 2). Under the
same reaction conditions, 1,4-bis(trimethylsilyl)-2-butyne (2b)
also underwent methylcyanation to give bis(silylmethyl)-sub-
stituted crotonitrile 3ab in 91% yield (Entry 3). Partial isomer-
ization of the initially formed cis-adduct was observed to give
a 12:88 mixture of E/Z stereoisomers. Methylcyanation of
unsymmetrical alkynes gave a single regioisomer but as a
mixture of stereoisomers (Entries 4-9). Addition to 1-phenyl-
1-propyne (2c) and 1-phenyl-1-butyne (2d) proceeded in
the presence of a slightly modified catalyst with PMe3 as a
ligand in acetonitrile as a solvent to give methylcyanation
products 3ac and 3ad in 53% and 49% yield, respectively
(Entries 4 and 5). In the latter case, E/Z ratio remained constant
throughout the reaction, implying a mechanism leading to
trans-adduct (vide infra). Silyl-substituted acetylenes 2e-2h
also underwent the methylcyanation reaction in the presence
of a Ni/PPhCy2/AlMe2Cl catalyst (Entries 6-9). Functional
groups such as ester, silyloxy, and internal double bond
were compatible with the reaction conditions. Formation of
formal trans-adducts was ascribed to isomerization of the
initial cis-adducts based on variable E/Z ratios during the
Results and Discussion
Nickel/Lewis Acid-Catalyzed Carbocyanation of
Alkynes Using Acetonitrile.
First, we investigated the
reaction of acetonitrile (1a) with 4-octyne (2a) in the presence
of a nickel/LA cooperative catalyst and found that AlMe3,
AlMe2Cl, and BPh3 were effective as a LA cocatalyst. After
Published on the web May 20, 2010; doi:10.1246/bcsj.20100023

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Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
Table 1. Nickel/Lewis Acid-Catalyzed Carbocyanation of Alkynes with Acetonitrile
Ni(cod)2 (5 mol %)
ligand (10 mol %)
LA (20 mol %)
Me
R1
CN
R2
R1
R2
+
Me CN
toluene, 80 °C
1a
2a–2h
3
(1.0 mmol)
Entry
1c)
Alkyne (mmol)
Cond.a)
Time/h
Major product, yield/%,b) E/Z
Me
CN
Pr
Pr
A
A
A
B
B
C
4
Pr
Pr
2a (10.0)
3aa, 71
D3C
CN
2d)
2a (1.0)
2b (1.0)
5
10
19
23
12
Pr
Pr
3aa-d3, 66e)
Me
CN
Me3Si
SiMe3
3
Me3Si
SiMe3
3ab, 91, 12:88f)
Me
CN
Me
Ph
4g)
5g)
6i)
Me
Ph
2c (1.0)
3ac, 53
Me
CN
Et
Ph
Et
Ph
2d (1.0)
3ad, 49, 61:39h)
Me
CN
Hex
SiMe3
Hex
SiMe3
2e (2.0)
3ae, 74, 9:91j)
Me
MeO2C
MeO2C
CN
7i)
8i)
9i)
C
C
C
21
24
24
SiMe3
SiMe3
SiMe3
SiMe3
2f (2.0)
2g (2.0)
2h (2.0)
3af, 38, 9:91
Me
t-BuMe2SiO
t-BuMe2SiO
CN
SiMe3
3ag, 60, 25:75
Me
CN
SiMe3
3ah, 63, 14:86
a) Conditions A, PPh2(t-Bu) and AlMe3; conditions B, PMe3 and AlMe3; conditions C, PPhCy2 and AlMe2Cl.
b) Isolated yields. c) Reaction run in a 10 mmol scale. d) d3-Acetonitrile was used. e) 99% Deuteration.
f) E/Z = 6:94 at 6 h. g) Reaction run with 1.0 mL of acetonitrile as a solvent. h) E/Z = 61:39 at 8 h. i) Run
with 10 mol % of Ni(cod)2. j) E/Z = 7:93 at 3 h.
reaction (Entries 6-9). The isomerization may be induced by
conjugate addition of a phosphorus ligand as a nucleophile. The
presence of a LA catalyst, which could interact with the cyano
group of the methylcyanation products, might further promote
the isomerization. Indeed, exposure of an isolated sample of
(Z)-3ae to the reaction conditions in the presence or absence of a
LA catalyst revealed such promotion of the isomerization.
Nickel/AlMe3-Catalyzed Carbocyanation Reaction of
Alkynes Using Propionitrile and Butyronitrile. We then
examined the reaction of propionitrile (1b) with 2a. Under the
optimal reaction conditions for the methylcyanation reaction,
no trace amount of ethylcyanation product 3ba was observed.
Instead, hydrocyanation product 4 was obtained in 3% yield
probably through ¢-hydride elimination from an ethylnickel

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
Table 2. Nickel/AlMe3-Catalyzed Carbocyanation of 4-Octyne with Propionitrile (1b)a)
621
Ni(cod)2 (x mol %)
ligand (2x mol %)
AlMe3 (4x mol %)
Et
Pr
CN
Pr
H
CN
Pr
+
+
Et CN
Pr
Pr
toluene, 8 h
Pr
1b
2a
(2.0 mmol)
4
3ba
(1.0 mmol)
L1: 2-C6H5–C6H4–PCy2
L2: 2-Mes–C6H4–PCy2
L3: 2-[2,6-(MeO)2–C6H3]–C6H4–PCy2
Product, yield/%b)
Entry
Ligand
x/mol %
Temp/°C
3ba
4
1
2
3
4
5
6
7
8
PPh2(t-Bu)
P(t-Bu)3
PCy3
L1
L2
L3
5
5
5
5
5
5
5
10
80
80
80
80
80
80
50
50
0
11
2
21
22
39
36
78c)
3
5
4
1
1
1
0
1
L3
L3
a) All the reaction was carried out using 1b (1.0 mmol) and 2a (2.0 mmol) in toluene (1.0 mL).
b) Estimated by GC using dodecane as an internal standard. c) Isolated yield.
Ni(cod)2 (10 mol %)
L3 (20 mol %)
AlMe3 (40 mol %)
intermediate (Entry 1 of Table 2). To suppress the unproduc-
tive ¢-hydride elimination and to optimize reaction conditions
for general alkylcyanation, we screened several ligands,
especially focusing on bulky phosphines (Entries 2-6). Of
the ligands examined, Buchwald’s ligands7 such as 2-Mes-
C6H4-PCy2 (L2)7b and 2-[2,6-(MeO)2-C6H3]-C6H4-PCy2
(L3)7c were found to be effective to give 3ba in modest yields
accompanied by small amounts of 4 (Entries 5 and 6). Use of
Ni(cod)2 (10 mol %) with L3 as a ligand at 50 °C significantly
improved yield of 3ba up to 78%, and only a trace amount of
4 was detected by GC (Entry 8). The improvement may be
attributed to lower reaction temperature and methoxy substitu-
ents in L3 that can coordinate to the nickel center of the
reaction intermediates to generate monophosphine nickel
species. Indeed, monitoring the reaction mixture by 31P NMR
showed free L3 in a significant amount (ca. 50%). Under the
same conditions, ethylcyanation of 2b also proceeded to give
the corresponding adduct 3bb in 83% yield, although partial
isomerization of the cis-adduct was again observed (eq 1).
Pr CN
1c
(1.0 mmol)
+
toluene, 50 °C, 30 h
Pr
Pr
2a
(2.0 mmol)
Pr
Pr
Pr
Pr
CN
Pr
H
CN
Pr
CN
Pr
+
+
ð2Þ
H
Pr
Pr
5, 15%
4, 19% (GC)
3ca, 10%
Dienyl cyanide 5 may be derived from 4 and 2a, because
isolated 4 reacted with 2a under the same reaction conditions to
give 5 through alkenylcyanaton of the alkyne.2d The observed
slow alkylcyanation reaction with 1c would result from ¢-
hydride elimination from a propylnickel intermediate to give a
propylene-nickel species, the alkene ligand of which would be
substituted by alkynes and/or produced 4 and 5 easily, whereas
the corresponding ethylene-nickel complex generated by ¢-
hydride elimination of an ethylnickel intermediate from 1b
would be stable enough to regenerate the ethylnickel species
through reinsertion of the coordinating ethylene to result in
better yield of the corresponding alkylcyanation product.
Nickel/AlMe2Cl-Catalyzed Carbocyanation of Alkynes
Using Arylacetonitriles. With the limited success in the
carbocyanation of alkynes with alkyl cyanides, we turned our
attention to the reaction of substituted acetonitriles, which
never suffer from ¢-hydride elimination. At the onset, we used
arylacetonitriles for carbocyanation, because relatively high
reactivity of the substrates was expected for the oxidative
addition of their C-CN bonds to nickel(0) as compared with
related reactions of allyl cyanides.2c,2g,8 After a brief survey
of reaction conditions with benzyl cyanide (1d, 1.0 mmol) and
4-octyne (2a, 1.0 mmol), we found that the combination of
Ni(cod)2 (2 mol %), L2 (4 mol %), and AlMe2Cl (8 mol %)
effectively catalyzed the desired benzylcyanation reaction at
35 °C to give 3da in 90% yield after 8 h (Entry 1 of Table 3).
Ni(cod)2 (10 mol %)
L3 (20 mol %)
AlMe3 (40 mol %)
Et CN
1b
(1.0 mmol)
+
toluene, 50 °C, 24 h
Me3Si
SiMe3
2b
(2.0 mmol)
Et
CN
Et
SiMe3
+
ð1Þ
Me3Si
SiMe3
Me3Si
CN
(Z)-3bb + (E)-3bb, 83%, 89:11
These results prompted us to examine the reaction of
butyronitrile (1c) with 2a under similar conditions. However,
an expected propylcyanation product was obtained only in
10% yield, and by-products 4 and 5 were obtained as major
components (eq 2).

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Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
Table 3. Carbocyanation of 4-Octyne with Arylacetonitriles
Ni(cod)2 (2 mol %)
L2 (4 mol %)
AlMe2Cl (8 mol %)
Ar
CN
Pr
+
Ar
1d–1p
(1.0 mmol)
CN
Pr
Pr
toluene
Pr
2a
(1.0 mmol)
3
Entry
1
Arylacetonitrile
Temp/°C
Time/h
Product, yield/%a)
CN
CN
R = H: 1d
35
35
80
35
8
3da, 90
3ea, 90
3fa, 74
3ga, 93
R
Pr
Pr
Pr
Pr
Pr
CN
Pr
Ph
Cl
2
3
4
Ph: 1e
8
18
8
CN
Pr
Cl: 1f
MeO
CN
Pr
MeO: 1g
O
O
O
CN
CN
O
CN
Pr
5
6
7
8
9
1h
35
80
35
80
35
24
5
3ha, 96
3ia, 56
3ja, 83
3ka, 85
3la, 85
Pr
CO2Me
R = CO2Me: 1i
CN
Pr
R
Pr
OMe
MeO: 1j
24
2
CN
Pr
Pr
Me
Me
1k
Me
CN
Pr
CN
Me
Me
Me Pr
CN
CN
Pr
1l
96
Pr
CN
CN
S
10
1m
1n
80
35
2
3ma, 95
3na, 54
Pr
Pr
S
CN
CN
Pr
11b)
10
N
N
H
H
Pr
CN
12b)
13b)
1o
1p
35
48
12
3oa, 69
3pa, 22
CN
Pr
HN
N
H
Pr
Ph
Ph
Ph
CN
Pr
100
Ph
CN
Pr
a) Isolated yields. b) The reaction was carried out using Ni(cod)2 (10 mol %), L2 (20 mol %), and AlMe2Cl (40 mol %).

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
623
Table 4. Carbocyanation of Alkynes with Phenylacetonitrile
Ni(cod)2 (2 mol %)
L2 (4 mol %)
AlMe2Cl (8 mol %)
Ph
CN
R2
NC
R1
Ph
+
+
Ph
CN
R1
R2
toluene
R1
R2
1d
2
3
3'
Product(s), yield/%,a) ratiob)
(1.0 mmol)
(1.0 mmol)
Entry
1
Alkyne
Temp/°C
Time/h
Ph
CN
Me3Si
SiMe3
80
70
Me3Si
SiMe3
2b
2i
3db, 93
Ph
CN
Ph
Ph
2
80
73
24
8
Ph
Ph
3di, 86c)
Ph
Ph
CN
NC
Ph
Ph
+
R2
3
R2 = Ph: 2c
35
35
35
35
35
35
35
Me
Me
Ph
Me
Ph
Et
3dc, 3′dc, 85, 92:8
CN
NC
+
4
Et: 2j
Me
Et
Me
3dj, 3′dj, 69, 59:41
Ph
Ph
Ph
CN
NC
Ph
+
5
t-Bu: 2k
SiMe3: 2l
21
53
11
Me
t-Bu
Me
t-Bu
3dk, 3′dk, 94, >99:1
CN
NC
Ph
+
6d)
Me
SiMe3
Me
SiMe3
3dl, 3′dl, 56, 81:19
CN
NC
Ph
H
+
7e)
R1 = Hex: 2m
R1
H
Hex
H
Hex
3dm, 3′dm, 48,f) 88:12
Ph
Ph
CN
NC
Ph
Ph
+
8e)
Cy: 2n
9
9
Cy
H
Cy
H
3dn, 3′dn, 61,f) 92:8
CN
NC
+
9e)
t-Bu: 2o
t-Bu
H
t-Bu
H
3do, 3′do, 54, >99:1
a) Isolated yields. b) Estimated by 1H NMR of a crude product. c) E/Z = 79:21 (82:18 at 1.5 h). d) The reaction was
carried out using Ni(cod)2 (10 mol %), L2 (20 mol %), and AlMe2Cl (40 mol %). e) The reaction was carried out using
3.0 equiv of alkyne, Ni(cod)2 (10 mol %), PMePh2 (20 mol %), and AlMe2Cl (40 mol %). f) 10-20% of an isomeric
mixture of 1:2 adducts were also detected.
We further studied the scope of benzyl cyanide having a
substituent on the phenyl ring and found that a range of
functional groups, such as chloro, acetal, and ester were
compatible with both the electron-rich nickel(0) and LA
catalysis, C-CN bonds being activated exclusively to give
various (Z)-3-arylmethyl-2,3-dipropylacrylonitriles (Entries 2-
9). Heteroarylacetonitriles also participated in the reaction
(Entries 10-12). Notably, no N-protecting group was necessary
for pyrrolyl- and indolylacetonitriles (Entries 11 and 12). The
sterically hindered C-CN bond in diphenylacetonitrile (1p) was
also activated to give the corresponding adduct 3pa having a
tertiary carbon albeit in a low yield (Entry 13).
The scope of alkynes toward benzyl cyanide (1d) is
summarized in Table 4. A symmetric alkyne, 1,4-bis(trimeth-
ylsilyl)-2-butyne (2b), participated in the benzylcyanation
reaction to afford 3db in 93% yield in an exclusive cis-fashion
(Entry 1), whereas the addition reaction across diphenylacety-
lene (2i) gave a mixture of stereoisomers (Entry 2). The

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Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
stereochemistry of (Z)-3di was unambiguously confirmed
by X-ray crystallography (Figure 1). Internal unsymmetrical
alkynes with sterically different substituents reacted with
modest to excellent regio- and stereoselectivities (Entries 3-
6). Whereas the regioselection across 2-pentyne (2j) was
modest because of small steric difference in the substituents
(Entry 4), 1-phenyl-1-propyne (2c), 4,4-dimethyl-2-pentyne
(2k), and trimethyl(1-propynyl)silane (2l) all reacted regio-
selectively to give preferentially isomers having a cyano group
at the carbon substituted by a larger group (Entries 3, 5, and 6).
Use of PMePh2 as a ligand allowed terminal alkynes to undergo
the benzylcyanation to give adducts in good to excellent
regioselectivity (Entries 7-9). In the presence of the nickel/L2
catalyst, tri- and/or oligomerization of terminal alkynes took
place rapidly, and no trace amount of the corresponding
benzylcyanation products was detected. In contrast to our
expectation, the observed regioselectivity was opposite to that
with internal alkynes, giving preferentially isomers with a
cyano group at the carbon having a smaller substituent
(hydrogen). This reversal of regiochemistry might be ascribed
to the difference of the ligand. However any of several
alternative explanations may be possible. Also observed was
formation of 10-20% of structurally unidentified 1:2 adducts,
when 2m and 2n were employed as an alkyne substrate.
Formation of the 1:2 adducts may be attributed to double
migratory insertion of 1-octyne into a C-Ni bond (vide infra)
based on the experimental fact that isolated 3dm did not react
with 2a under the same reaction conditions. In all cases, ratios
of regioisomers 3:3¤ were constant during the reaction course,
suggesting that these adducts should be kinetic products (vide
infra).
Figure 1. ORTEP drawing for (Z)-3di.
Table 5. Carbocyanation of Alkynes with Protected Functionalized Acetonitriles
Ni(cod)2 (5 mol %)
ligand (10 mol %)
BPh3 (20 mol %)
FG
CN
NC
R1
FG
R1
R2
+
+
FG
CN
toluene, 80 °C
R1
R2
R2
1q–1s
(1.0 mmol)
2
3
3'
ligand:
(2.0 mmol)
P(3,5-Me2–4-MeO–C6H2)3 (L4)
P(4-MeO–C6H4)3 (L5)
P(c-Pent)3 (L6)
Entry
1
Nitrile
Alkyne
Ligand
Time/h
Product(s), yield/%,a) ratiob)
O
PhthN
CN
Pr
N
Pr
Pr
L4
30
CN
Pr
2a
2c
O
3qa, 64c)
1q
PhthN
PhthN
CN
NC
NPhth
NPhth
+
Me
Me
Ph
2
3
1q
1q
L4
L4
30
30
Me
Me
Ph
Me
Ph
3qc, 3′qc, 60,c) 92d):8
CN
NC
+
t-Bu
t-Bu
Me
t-Bu
2k
3qk, 3′qk, 79, >99:1
THPO
CN
4e),f)
2a
L5
L6
3
O
O
CN
Pr
Pr
3ra, 82c)
1r
Me3Si
CN
Me3Si
CN
5f)
2a
13
Pr
Pr
1s
3sa, 89
a) Isolated yields. b) Estimated by 1H NMR of a crude product. c) An isomeric mixture of 1:2 adducts (10-20%) also
was detected. d) E/Z = 13:87 (5:95 at 6 h). e) The reaction was carried out using Ni(cod)2 (10 mol %), L5 (20 mol %),
and BPh3 (40 mol %). f) 2a (1.5 mmol) was used.

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
625
Ni(cod)2 (20 mol %)
2-(2,4,6-i-Pr3–C6H2)–C6H4–PCy2 (40 mol %)
AlMe2Cl (20 mol %)
Nickel/BPh3-Catalyzed Carbocyanation of Alkynes
Using Functionalized Acetonitriles. Having established a
broad scope of the carbocyanation of alkynes with arylaceto-
nitriles, we next examined the reaction using other function-
alized acetonitriles. We envisioned that the addition of amino-
and alkoxyacetonitriles across alkynes would straightforwardly
give highly functionalized polysubstituted allylic amines and
alcohols with defined stereochemistry. To verify this strategy,
we first examined the reaction of N-(cyanomethyl)phthalimide
(1q) with 4-octyne (2a). After brief screening of ligands and
LA using Ni(cod)2 (5 mol %) in toluene at 80 °C, we found
the combination of P(3,5-Me2-4-MeO-C6H2)3 (10 mol %) and
BPh3 (20 mol %) was the best, and obtained protected trisub-
stituted (Z)-allylic amine 3qa in 64% yield (Entry 1 of
Table 5). Unsymmetrical alkynes, 2c and 2k, also underwent
the addition of 1q with the same regioselectivity observed for
the benzylcyanation reaction (Entries 2 and 3). In the case of 1-
phenyl-1-propyne (2c), a small amount of stereoisomer (E)-3qc
was obtained, which should be derived from isomerization
of initially formed (Z)-3qc. Indeed, exposure of the isolated
sample of (Z)-3qc to the present reaction conditions caused the
isomerization. THP-protected hydroxyacetonitrile (1r) also
served as a substrate of the alkyne-carbocyanation reaction
under slightly modified conditions to give the corresponding
THP-protected allylic alcohol 3ra in a stereoselective manner
(Entry 4). For silylmethylcyanation of 2a with (trimethylsilyl)-
acetonitrile (1s), a BPh3 cocatalyst was more effective than
AlMe2Cl,2d possibly because the milder Lewis-acidity of BPh3
is favorable for the reactions of particular nitriles 1q-1s that
give products with acid-sensitive functional groups.
+
2a
Ph
CN
toluene, 80 °C, 0.5 h
(S)-1t, 85% ee (5.0 equiv)
83% conv. of 1t
CN
H
+
CN
Pr
Ph
CN
Pr
+
+
ð3Þ
Ph
Pr
Ph
Pr
(S)-3ta, 22%, 41% ee
4, 35% (GC) 6, 44% (GC) 7, 3% (GC)
NaIO4
•
RuCl3 3H2O cat.
Ph
(S)-8, 43%, 38% ee, [α]3D0 114 (c 0.555, toluene)
O
Pr
The corresponding adduct (S)-3ta of 41% ee was obtained in
22% yield, the absolute configuration being determined based
on the reported optical rotation of (R)-2-phenyl-3-hexanone
[(R)-8]9 after oxidative cleavage of the double bond. Also
obtained were hydrocyanation product 4, styrene (6), and
hydrocinnamonitrile (7) in 35%, 44%, and 3% yields,
respectively, as estimated by GC. Recovered 1t showed 80%
ee, suggesting that background racemization of 1t under these
conditions appears to be slower than the carbocyanation event.
We also confirmed that no further racemization of 3ta took
place under the present conditions. Accordingly, these results
clearly suggest a mechanism shown in Scheme 1, which should
start with oxidative addition of a C-CN bond with retention of
configuration through LA adduct of ©2-nitrile-nickel species
A4e to give B.5d Oxidative addition of acetonitrile to nickel(0)
with retention of configuration has also been suggested by
theoretical calculations,5j in contrast to the nonstereospecific
oxidative addition of benzyl halides to nickel(0).10 The details
of the mechanism may be understood in terms of the following
steps. Coordination and then migratory insertion of alkynes
into the ArC(R)H-Ni bond in B give D via C. Reductive
elimination from D gives rise to a carbocyanation product and
regenerates nickel(0) species. The absolute configuration is
retained during these elemental steps.11 The partial loss of % ee
during the addition reaction may be ascribed to ¢-hydride
Reaction Mechanism.
To gain stereochemical and
mechanistic insight, (S)-¡-phenylpropionitrile [(S)-1t] of 85%
enantiomeric excess (ee) was reacted with 2a under slightly
modified conditions using Ni(cod)2 (20 mol %), 2-(2,4,6-i-Pr3-
C6H2)-C6H4-PCy2 (L7, 40 mol %),7d and AlMe2Cl (20 mol %)
(eq 3).
R
R
Ar
R1
Ar
R1
R2
NC
R2
R
L
L
Ni(0)
+
NC
Ar
NC
trans-adduct
cis-adduct
LA
R
L
R
R
L
Ni
LA–NC
LA
N
C
Ar
Ar
R1
Ar
R1
R2
Ni
A
L
L
LA–NC
Ni
R2
R2 = Ph
L = P-ligand
L
D
L
LA = AlMe2Cl
E
retention
R
Ph
R
7
+
L
H
L
Ph
Ar
R1
L
L
Ar
L2Ni(0)
+
LA
Ni
L
L
Ni
Ni
LA–NC
Ni
CN–LA
CN–LA
B
Ar = Ph
R = Me
CN–LA
R2
R2
2
2
C
2
6
6
R2
4
+
H
H
L
L2Ni(0)
+
LA
L
L
R1
R1
CN–LA
Ni
Ni
CN–LA
Scheme 1. Plausible mechanism.

626
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
elimination followed by reinsertion. Particularly, the formation
of 4 as well as 6 and 7 is in accord with these possible
side reactions. A small degree of racemization observed in
recovered 1t suggests that reductive elimination from sec-
alkyl(cyano)nickel intermediate B to regenerate 1t would be
slower than that from alkenyl- or alkyl(cyano)nickel inter-
mediates giving adducts and alkyl cyanide 7 due presumably to
steric repulsion by the phenyl substituent. On the other hand,
migratory insertion of the sec-alkyl group would be much faster
than that of the 2-phenylethyl group, because no detectable
amount of (2-phenylethyl)cyanation was observed. In the case
of phenyl-substituted alkynes, D may isomerize to E possibly
through conjugate addition of phosphorus ligands12 followed
by reductive elimination to give trans-adduct. A LA catalyst
would primarily accelerate the oxidative addition step,2d,4e,4f,8a
although other elemental steps may also be facilitated by its
coordination to a cyano group.13
MP-500D. Elemental analyses were performed by Elemental
Analysis Center of Kyoto University. Chiral HPLC analyses
were performed with a Shimadzu Prominence chromatograph.
Optical rotations were measured on a JASCO DIP-360. High-
resolution mass spectra were obtained with a JEOL JMS-700
(EI). X-ray crystal data were collected with a Bruker SMART
APEX diffractometer [for (Z)-3di]. Preparative recycling
silica gel chromatography was performed with a JAI LC-908
chromatograph equipped with Nacalai Tesque 5SL-II (hexane-
ethyl acetate as an eluent). 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.14 2-Mes-
C6H4-PCy2 (L2),7b 2-(2,4,6-i-Pr3-C6H2)-C6H4-PCy2 (L7),7d
1,4-bis(trimethylsilyl)-2-butyne (2b),15 2-pyrrolylacetonitrile
(1n),16 (S)-¡-phenylpropionitrile [(S)-1t] (using (R,S)-Josiphos
as a ligand),17 N-(cyanomethyl)phthalimide (1q),18 and tetra-
hydro-2H-pyran-2-yloxyacetonitrile (1r)19 were prepared ac-
cording to the respective literature procedure.
Conclusion
In summary, we have demonstrated the nickel/Lewis acid-
catalyzed methylcyanation of alkynes proceeds with high cis-
selectivity and high regioselectivity. Extension of this catalysis
to propionitrile as an alkyl cyanide substrate also meets success
by employing bulky phosphorous ligand L3 having a hemi-
labile methoxy group, whereas propylcyanation reaction of 4-
octyne using butyronitrile proceeded only sluggishly even with
the improved catalyst system due to competitive ¢-hydride
elimination. Instead, a general substrate scope of the carbocya-
nation reaction with arylacetonitriles has been established
under mild reaction conditions with nickel/AlMe2Cl catalysts.
Moreover, functionalized acetonitriles such as protected amino-
and hydroxyacetonitriles as well as silylacetonitrile have been
demonstrated to add across alkynes in stereo- and regioselec-
tive manners under nickel/BPh3 catalysis, producing a wide
variety of polysubstituted acrylonitriles having allylic func-
tional groups. Using (S)-¡-phenylpropionitrile, the mechanism
of the carbocyanation including the oxidative addition of C-
CN bonds with retention of configuration has been elucidated.
Methyl 6-Trimethylsilyl-5-hexynoate (2f).
A 1.6 M
solution of n-BuLi (34 mmol, 22 mL) in hexane was added
dropwise to a solution of methyl 5-hexynoate (3.6 g, 29 mmol)
in THF (29 mL) at ¹78 °C, and the resulting mixture was
stirred for 30 min before dropwise addition of chlorotrimethyl-
silane (3.4 g, 32 mmol). The reaction mixture was stirred at rt
for 19 h before quenching with a saturated NH4Cl aqueous
solution. The resulting mixture was extracted three times
with diethyl ether, and the combined organic layers were
dried over anhydrous MgSO4, filtered through a Celite pad, and
then concentrated in vacuo. The residue was purified by flash
column chromatography on silica gel (hexane-ethyl acetate =
30:1) and further by distillation under vacuum to give the title
compound (1.12 g, 5.7 mmol, 20%).20
Experimental
General.
All manipulations of oxygen- and moisture-
5-tert-Butyldimethylsilyloxy-1-trimethylsilyl-1-pentyne
(2g). To a suspension of NaH (0.86 g, 36 mmol) in THF
(150 mL) was added dropwise 4-pentyn-1-ol (2.8 g, 33 mmol) at
0 °C. The resulting mixture was stirred at rt for 30 min, cooled
at 0 °C, and treated with tert-butylchlorodimethylsilane (5.4 g,
30 mmol). The whole mixture was stirred at rt for 15 h, and then
quenched with water. The resulting mixture was extracted three
times with hexane, and the combined organic layers were
washed three times with water, dried over anhydrous MgSO4,
filtered through a Celite pad, and then concentrated in vacuo.
The residue was purified by flash column chromatography on
silica gel (hexane-ethyl acetate = 50:1) to give 1-tert-butyldi-
methylsilyloxy-4-pentyne (3.6 g, 18.3 mmol, 61%).21 To a
solution of the silyl ether (3.6 g, 18.3 mmol) in THF (37 mL)
was added dropwise a 1.6 M solution of n-BuLi (20 mmol,
13 mL) in hexane at ¹78 °C. The resulting mixture was stirred
for 30 min before dropwise addition of chlorotrimethylsilane
(2.4 g, 22.0 mmol). After stirring at rt for 13 h, the reaction
was quenched with a saturated NH4Cl aqueous solution. The
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-
eter with solvent resonance as the internal standard (1H NMR,
CHCl3 at 7.26 ppm; 13C NMR, CDCl3 at 77.0 ppm). H NMR
data are reported as follows: chemical shift, spin multiplicity
(s = singlet, d = doublet, t = triplet, q = quartet, quint =
quintet, sext = sextet, br = broad, m = multiplet), coupling
constants (Hz), and integration. Infrared spectra (IR) recorded
on a Shimadzu FTIR-8400 spectrometer are reported in cm
1
¹1
.
Melting points (mp) were determined using a YANAKO

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
listed in Table 1.
627
resulting mixture was extracted three times with hexane, and
the combined organic layers were washed three times with
water, dried over anhydrous MgSO4, filtered through a Celite
pad, and then concentrated in vacuo. The residue was purified
by distillation under vacuum to give the title compound (4.5 g,
16.6 mmol, 90%).22
(E)-6,10-Dimethyl-1-trimethylsilyl-5,9-undecadien-1-yne
(2h). A 1.6 M solution of n-BuLi (24 mmol, 15 mL) in hexane
was added dropwise to a solution of (E)-6,10-dimethyl-5,9-
undecadien-1-yne (3.5 g, 20 mmol, prepared23 from (E)-1-
chloro-3,7-dimethyl-2,6-octadiene) in THF (40 mL) at
¹78 °C, and the resulting mixture was stirred for 15 min before
dropwise addition of chlorotrimethylsilane (3.3 g, 30 mmol).
After stirring at rt for 3 h, the reaction was quenched with
water. The resulting mixture was extracted three times with
hexane, and the combined organic layers were washed three
times with water, dried over anhydrous MgSO4, filtered
through a Celite pad, and then concentrated in vacuo. The
residue was purified by distillation under vacuum to give the
title compound (4.6 g, 18.5 mmol, 92%).24
General procedure C: In a dry box, acetonitrile (82 mg,
2.0 mmol), a 1.0 M solution of AlMe2Cl in hexane (0.40 mL,
0.40 mmol), an alkyne (1.00 mmol), and dodecane (internal
standard, 85 mg, 0.50 mmol) were added sequentially to a
solution of Ni(cod)2 (28 mg, 0.10 mmol) and PPhCy2 (55 mg,
0.20 mmol) in toluene (1.0 mL) placed in a vial. The vial was
taken out from the dry box and heated at 80 °C for the time
specified in Table 1. The resulting mixture was filtered through
a silica gel pad, concentrated in vacuo, and purified by flash
silica gel column chromatography to give the corresponding
alkylcyanation products in yields listed in Table 1.
Regio- and/or stereoisomers were separated by preparative
GPC or HPLC and characterized by spectrometry. The spectra
of 3ac and 3ad agreed well with those reported previously.25
(E)-3-(2H3)Methyl-2-propylhex-2-enenitrile (3aa-d3):
colorless oil, Rf = 0.20 (hexane-ethyl acetate = 40:1).
1H NMR (400 MHz, CDCl3): ¤ 0.92 (t, J = 7.3 Hz, 3H), 0.94
(t, J = 7.3 Hz, 3H), 1.45 (sext, J = 7.5 Hz, 2H), 1.55 (sext,
J = 7.5 Hz, 2H), 2.11-2.21 (m, 4H); 13C NMR (101 MHz,
CDCl3): ¤ 13.6, 14.1, 21.0, 21.9, 31.5, 35.5, 109.7, 119.3,
155.2. IR (neat): 2963, 2934, 2874, 2208, 1624, 1466, 1381,
1090, 1042, 739 cm¹1. HRMS (EI) Calcd for C10H14D3N: M+,
154.1549. Found: m/z 154.1557.
A
Methylcyanation of 4-Octyne (2a).
In a dry box,
acetonitrile (1a, 0.41 g, 10.0 mmol), a 1.0 M solution of AlMe3
in hexane (2.0 mL, 2.0 mmol), and 2a (1.10 g, 10.0 mmol)
were added sequentially to a solution of Ni(cod)2 (138 mg,
0.50 mmol) and PPh2(t-Bu) (0.24 g, 1.00 mmol) in toluene
(10 mL) placed in a vial. The resulting mixture was stirred at
80 °C for 4 h, filtered through a silica gel pad, and concentrated
in vacuo. The residue was distilled to give (E)-3-methyl-2-
propylhex-2-enenitrile (3aa, 1.08 g, 71%) as a pale yellow oil,
bp 80 °C (20 mmHg), Rf = 0.18 (hexane-ethyl acetate = 40:1).
1H NMR (400 MHz, CDCl3): ¤ 0.93 (t, J = 7.3 Hz, 3H), 0.94
(t, J = 7.3 Hz, 3H), 1.46 (sext, J = 7.5 Hz, 2H), 1.56 (sext,
J = 7.5 Hz, 2H), 2.05 (s, 3H), 2.12-2.21 (m, 4H); 13C NMR
(101 MHz, CDCl3): ¤ 13.6, 14.1, 21.0, 21.9, 22.6, 31.5, 35.6,
109.7, 119.3, 155.3. IR (neat): 2964, 2934, 2874, 2208, 1630,
1466, 1381, 1138, 1094, 741 cm¹1. Anal. Calcd for C10H17N;
C, 79.41; H, 11.33%. Found: C, 79.47; H, 11.47%.
Carbocyanation of Alkynes with Acetonitrile. General
procedure A: In a dry box, acetonitrile (41 mg, 1.00 mmol), a
1.0 M solution of AlMe3 in hexane (0.20 mL, 0.20 mmol), an
alkyne (1.00 mmol), and dodecane (internal standard, 85 mg,
0.50 mmol) were added sequentially to a solution of Ni(cod)2
(14 mg, 50 ¯mol) and PPh2(t-Bu) (24 mg, 0.10 mmol) in
toluene (1.0 mL) placed in a vial. The vial was taken out from
the dry box and heated at 80 °C for the time specified in
Table 1. The resulting mixture was filtered through a silica gel
pad, concentrated in vacuo, and purified by flash silica gel
column chromatography to give the corresponding alkylcyana-
tion products in yields listed in Table 1.
(Z)-3-Methyl-4-(trimethylsilyl)-2-[(trimethylsilyl)methyl]-
but-2-enenitrile [(Z)-3ab]:
A colorless oil, Rf = 0.20
1
(hexane-ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤
0.09 (s, 9H), 0.11 (s, 9H), 1.56 (s, 2H), 1.70 (s, 2H), 2.04 (s,
3H); 13C NMR (101 MHz, CDCl3): ¤ ¹1.1, ¹0.4, 21.0, 24.8,
27.4, 102.1, 120.8, 151.2. IR (neat): 2955, 2899, 2205, 1614,
1418, 1250, 1196, 1175, 1144, 1086, 1011, 928, 845, 762, 696,
627, 606, 594, 565, 478, 442 cm¹1. Anal. Calcd for C12H25-
NSi2: C, 60.18; H, 10.52%. Found: C, 60.09; H, 10.62%.
(E)-3-Methyl-4-(trimethylsilyl)-2-[(trimethylsilyl)methyl]-
but-2-enenitrile [(E)-3ab]:
A pale yellow oil, Rf = 0.20
1
(hexane-ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤
0.11 (s, 9H), 0.12 (s, 9H), 1.64 (s, 2H), 1.75 (s, 3H), 2.02 (s,
2H); 13C NMR (101 MHz, CDCl3): ¤ ¹1.1, ¹0.4, 21.0, 21.2,
31.1, 102.2, 121.1, 151.1. IR (neat): 2955, 2899, 2207, 1614,
1416, 1377, 1248, 1179, 1152, 1096, 1015, 920, 841, 762,
694 cm¹1. HRMS (EI) Calcd for C12H25NSi2: M+, 239.1526.
Found: m/z 239.1521.
(Z)-3-Methyl-2-trimethylsilylnon-2-enenitrile [(Z)-3ae]:
A colorless oil, Rf = 0.15 (hexane-ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3): ¤ 0.28 (s, 9H), 0.90 (t, J = 6.9
Hz, 3H), 1.24-1.37 (m, 6H), 1.40-1.50 (m, 2H), 2.15 (s, 3H),
2.25 (t, J = 8.0 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 0.1,
14.1, 22.6, 24.4, 28.4, 29.5, 31.7, 38.7, 108.7, 120.3, 174.2. IR
(neat): 2957, 2930, 2858, 2197, 1583, 1466, 1377, 1254, 843,
762 cm¹1. Anal. Calcd for C13H25NSi: C, 69.88; H, 11.28%.
Found: C, 69.81; H, 11.42%.
General procedure B: In a dry box, a 1.0 M solution of
AlMe3 in hexane (0.20 mL, 0.20 mmol), an alkyne (1.00
mmol), and dodecane (internal standard, 85 mg, 0.50 mmol)
were added sequentially to a solution of Ni(cod)2 (14 mg, 50
¯mol) and PMe3 (7.6 mg, 0.10 mmol) in acetonitrile (1.0 mL)
placed in a vial. The vial was taken out from the dry box and
heated at 80 °C for the time specified in Table 1. The resulting
mixture was filtered through a silica gel pad, concentrated in
vacuo, and purified by flash silica gel column chromatography
to give the corresponding alkylcyanation products in yields
(E)-3-Methyl-2-trimethylsilylnon-2-enenitrile [(E)-3ae]:
A colorless oil, Rf = 0.15 (hexane-ethyl acetate = 30:1).
1H NMR (400 MHz, CDCl3): ¤ 0.29 (s, 9H), 0.89 (t, J = 6.9
Hz, 3H), 1.26-1.39 (m, 6H), 1.46-1.55 (m, 2H), 1.97 (s, 3H),
2.49 (t, J = 7.8 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ ¹0.2,
14.2, 22.56, 22.63, 28.1, 29.1, 31.7, 41.0, 108.3, 120.0, 174.2.
IR (neat): 2957, 2930, 2858, 2195, 1583, 1462, 1377, 1254,
843, 760 cm¹1. Anal. Calcd for C13H25NSi: C, 69.88; H,

628
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
11.28%. Found: C, 69.98; H, 11.08%.
CDCl3): ¤ ¹0.3, 16.2, 17.8, 22.9, 25.8, 26.7, 26.8, 39.8, 40.8,
108.8, 119.9, 122.2, 124.1, 131.3, 136.6, 173.5. IR (neat):
2963, 2918, 2857, 2193, 1584, 1451, 1375, 1254, 1109, 1042,
843, 760, 696, 644, 629 cm¹1. HRMS (EI) Calcd for
C18H31NSi: M+, 289.2226. Found: m/z 289.2225.
(Z)-Methyl
6-Cyano-5-methyl-6-trimethylsilylhex-5-
enoate [(Z)-3af]: A colorless oil, Rf = 0.25 (hexane-ethyl
acetate = 5:1). 1H NMR (400 MHz, CDCl3): ¤ 0.28 (s, 9H),
1.79 (quint, J = 7.7 Hz, 2H), 2.17 (s, 3H), 2.30 (t, J = 8.1 Hz,
2H), 2.34 (t, J = 7.3 Hz, 2H), 3.68 (s, 3H); 13C NMR (101
MHz, CDCl3): ¤ 0.0, 23.4, 24.2, 33.6, 37.6, 51.7, 110.1, 120.0,
172.3, 172.8. IR (neat): 2955, 2901, 2195, 1740, 1584, 1437,
1375, 1254, 1200, 1157, 1088, 1045, 1007, 905, 843, 762, 698,
631 cm¹1. Anal. Calcd for C12H21NO2Si: C, 60.21; H, 8.84%.
Found: C, 59.99; H, 8.69%.
Ethylcyanation of Alkynes Using Propionitrile (Entry 8
of Table 2 and eq 1). General procedure: In a dry box,
propionitrile (60 mg, 1.00 mmol), a 1.0 M solution of AlMe3 in
hexane (0.40 mL, 0.40 mmol), an alkyne (2.00 mmol), and
dodecane (internal standard, 85 mg, 0.50 mmol) were added
sequentially to a solution of Ni(cod)2 (28 mg, 0.10 mmol) and
2-[2,6-(MeO)2-C6H3]-C6H4-PCy2 (82 mg, 0.20 mmol) in tol-
uene (1.0 mL) placed in a vial. The vial was taken out from the
dry box and heated at 50 °C for 8 h (for 2a) or 24 h (for 2b).
The resulting mixture was filtered through a silica gel pad,
concentrated in vacuo, and purified by flash column chroma-
tography on silica gel to give the corresponding carbocyanation
products in yields listed in Entry 8 of Table 2 and eq 1.
Stereoisomers were separated by preparative HPLC and
characterized by spectrometry.
(Z)-3-Ethyl-2-propylhex-2-enenitrile (3ba): A colorless
oil, Rf = 0.18 (hexane-ethyl acetate = 40:1). 1H NMR (400
MHz, CDCl3): ¤ 0.940 (t, J = 7.3 Hz, 3H), 0.944 (t, J = 7.3 Hz,
3H), 1.09 (t, J = 7.6 Hz, 3H), 1.43 (sext, J = 7.6 Hz, 2H), 1.57
(sext, J = 7.4 Hz, 2H), 2.15 (t, J = 7.9 Hz, 2H), 2.17 (t, J =
7.3 Hz, 2H), 2.40 (q, J = 7.5 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 13.2, 13.6, 14.3, 21.4, 21.9, 29.3, 31.5, 33.0, 109.2,
119.1, 161.1. IR (neat): 2964, 2936, 2874, 2208, 1624, 1464,
1379, 1138, 1057, 797, 741 cm¹1. Anal. Calcd for C11H19N: C,
79.94; H, 11.59%. Found: C, 79.91; H, 11.71%.
(E)-Methyl
6-Cyano-5-methyl-6-trimethylsilylhex-5-
enoate [(E)-3af]: A colorless oil, Rf = 0.25 (hexane-ethyl
acetate = 5:1). 1H NMR (400 MHz, CDCl3): ¤ 0.29 (s, 9H),
1.86 (quint, J = 7.7 Hz, 2H), 1.99 (s, 3H), 2.37 (t, J = 7.5 Hz,
2H), 2.54 (t, J = 7.8 Hz, 2H), 3.69 (s, 3H); 13C NMR (101
MHz, CDCl3): ¤ ¹0.3, 22.4, 23.2, 33.4, 40.0, 51.7, 109.7,
119.7, 172.4, 173.2. IR (neat): 2955, 2195, 1740, 1586, 1437,
1375, 1254, 1200, 1175, 1157, 1088, 1045, 1003, 845, 762,
698, 640 cm¹1. HRMS (EI) Calcd for C12H21NO2Si: M+,
239.1342. Found: m/z 239.1343.
(Z)-6-(tert-Butyldimethylsilyloxy)-3-methyl-2-trimethyl-
silylhex-2-enenitrile [(Z)-3ag]: A colorless oil, Rf = 0.10
1
(hexane-ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤
0.06 (s, 6H), 0.29 (s, 9H), 0.90 (s, 9H), 1.60-1.70 (m, 2H), 2.17
(s, 3H), 2.35 (t, J = 8.1 Hz, 2H), 3.65 (t, J = 5.9 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ ¹5.2, 0.0, 18.4, 24.5, 26.0,
31.5, 35.4, 62.7, 109.1, 120.3, 173.8. IR (neat): 2955, 2930,
2897, 2858, 2197, 1583, 1472, 1462, 1437, 1408, 1387, 1362,
1256, 1099, 1022, 1005, 947, 908, 839, 777, 762, 696, 662,
629 cm¹1. Anal. Calcd for C16H33NOSi2: C, 61.67; H, 10.67%.
Found: C, 61.51; H, 10.66%.
(Z)-2,3-Bis(trimethylsilylmethyl)pent-2-enenitrile [(Z)-
3bb]:
A colorless oil, Rf = 0.16 (hexane-ethyl acetate =
(E)-6-(tert-Butyldimethylsilyloxy)-3-methyl-2-trimethyl-
silylhex-2-enenitrile [(E)-3ag]: A colorless oil, Rf = 0.13
(hexane-ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤
0.07 (s, 6H), 0.29 (s, 9H), 0.91 (s, 9H), 1.69-1.77 (m, 2H), 2.00
(s, 3H), 2.55 (t, J = 8.0 Hz, 2H), 3.65 (t, J = 6.4 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ ¹5.1, ¹0.3, 18.4, 22.7, 26.0,
31.3, 37.5, 62.5, 108.7, 119.8, 173.8. IR (neat): 2955, 2930,
2897, 2858, 2195, 1585, 1472, 1462, 1408, 1389, 1362, 1254,
1103, 1007, 839, 775, 760 cm¹1. Anal. Calcd for C16H33NOSi2:
C, 61.67; H, 10.67%. Found: C, 61.95; H, 10.75%.
30:1). 1H NMR (400 MHz, CDCl3): ¤ 0.09 (s, 9H), 0.11 (s, 9H),
1.10 (t, J = 7.5 Hz, 3H), 1.55 (s, 2H), 1.70 (s, 2H), 2.34 (q,
J = 7.5 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ ¹1.1, ¹0.4,
13.7, 21.0, 24.5, 31.2, 101.3, 120.6, 157.5. IR (neat): 2955,
2899, 2203, 1607, 1464, 1418, 1400, 1375, 1250, 1184, 1173,
1142, 1063, 1044, 978, 912, 843, 791, 772, 696, 673, 606,
525 cm¹1. Anal. Calcd for C13H27NSi2: C, 61.59; H, 10.73%.
Found: C, 61.76; H, 10.99%.
1
(E)-2,3-Bis(trimethylsilylmethyl)pent-2-enenitrile [(E)-
3bb]:
A colorless oil, Rf = 0.16 (hexane-ethyl acetate =
1
(2Z,6E)-3,7,11-Trimethyl-2-trimethylsilyldodeca-2,6,10-
trienenitrile [(Z)-3ah]: A colorless oil, Rf = 0.18 (hexane-
30:1). H NMR (400 MHz, CDCl3): ¤ 0.12 (s, 18H), 1.01 (t,
J = 7.5 Hz, 3H), 1.64 (s, 2H), 2.00 (s, 2H), 2.06 (q, J = 7.5 Hz,
2H); 13C NMR (101 MHz, CDCl3): ¤ ¹1.1, ¹0.5, 12.0, 20.4,
26.7, 27.6, 101.5, 121.3, 156.7. IR (neat): 2955, 2895, 2205,
1605, 1452, 1418, 1244, 1171, 1150, 1069, 1038, 976, 905,
839, 791, 766, 704, 694, 648 cm¹1. HRMS (EI) Calcd for
C13H27NSi2: M+, 253.1682. Found: m/z 253.1694.
1
ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤ 0.29 (s,
9H), 1.61 (s, 3H), 1.62 (s, 3H), 1.69 (s, 3H), 1.97-2.11 (m, 4H),
2.14-2.22 (m, 2H), 2.18 (s, 3H), 2.30 (t, J = 8.0 Hz, 2H), 5.02-
5.11 (m, 2H); 13C NMR (101 MHz, CDCl3): ¤ 0.1, 16.2, 17.8,
24.3, 25.9, 26.6, 26.8, 38.5, 39.7, 109.3, 120.2, 122.1, 123.9,
131.4, 136.5, 173.5. IR (neat): 2965, 2916, 2857, 2195, 1667,
1582, 1445, 1377, 1327, 1254, 1109, 1042, 984, 893, 843, 760,
696, 629 cm¹1. Anal. Calcd for C18H31NSi: C, 74.67; H,
10.79%. Found: C, 74.76; H, 11.01%.
Propylcyanation of 2a Using Butyronitrile (eq 2). In a
dry box, butyronitrile (69 mg, 1.00 mmol), a 1.0 M solution of
AlMe3 in hexane (0.40 mL, 0.40 mmol), 4-octyne (220 mg, 2.00
mmol), and dodecane (internal standard, 85 mg, 0.50 mmol)
were added sequentially to a solution of Ni(cod)2 (28 mg, 0.10
mmol) and 2-[2,6-(MeO)2-C6H3]-C6H4-PCy2 (82 mg, 0.20
mmol) in toluene (1.0 mL) placed in a vial. The vial was taken
out from the dry box and heated at 50 °C for 30 h. GC analysis of
the reaction mixture showed the formation of hydrocyanation
product 4 in 19% yield. The mixture was filtered through a silica
(2E,6E)-3,7,11-Trimethyl-2-trimethylsilyldodeca-2,6,10-
trienenitrile [(E)-3ah]: A colorless oil, Rf = 0.23 (hexane-
1
ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤ 0.29 (s,
9H), 1.61 (s, 3H), 1.62 (s, 3H), 1.69 (s, 3H), 1.96-2.02 (m, 2H),
1.98 (s, 3H), 2.04-2.12 (m, 2H), 2.23 (q, J = 7.4 Hz, 2H), 2.53
(t, J = 7.6 Hz, 2H), 5.06-5.17 (m, 2H); 13C NMR (101 MHz,

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
629
gel pad, concentrated in vacuo, and purified by flash column
chromatography on silica gel followed by preparative HPLC to
give 2,3-dipropylhex-2-enenitrile (3ca, 18 mg, 10%) and the
isomeric mixture of 1:2 adducts (38 mg, 15%).
127.3, 128.7, 129.1, 136.9, 139.6, 140.7, 157.7. IR (neat):
3028, 2963, 2932, 2872, 2361, 2343, 2206, 1487, 1458, 1408,
1381, 1009, 910, 735, 698, 421 cm¹1. Anal. Calcd for
C22H25N: C, 87.08; H, 8.30%. Found: C, 87.34; H, 8.36%.
(Z)-3-[(4-Chlorophenyl)methyl]-2-propylhex-2-enenitrile
2,3-Dipropylhex-2-enenitrile (3ca):
A colorless oil,
1
Rf = 0.10 (hexane-ethyl acetate = 30:1). H NMR (400 MHz,
CDCl3): ¤ 0.94 (t, J = 7.3 Hz, 3H), 0.95 (t, J = 7.4 Hz, 3H),
0.96 (t, J = 7.3 Hz, 3H), 1.43 (sext, J = 7.5 Hz, 2H), 1.52 (sext,
J = 7.5 Hz, 2H), 1.58 (sext, J = 7.5 Hz, 2H), 2.14 (t, J = 7.9
Hz, 2H), 2.19 (t, J = 7.6 Hz, 2H), 2.38 (t, J = 7.6 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 13.6, 14.0, 14.3, 21.5, 21.8,
21.9, 31.6, 33.4, 38.0, 110.0, 119.3, 159.4. IR (neat): 2963,
2934, 2874, 2207, 1624, 1458, 1381, 1341, 1258, 1136, 1094,
1076, 895, 743 cm¹1. Anal. Calcd for C12H21N: C, 80.38; H,
11.81%. Found: C, 80.41; H, 11.61%.
(3fa):
A colorless oil, Rf = 0.34 (hexane-ethyl acetate =
1
10:1). H NMR (400 MHz, CDCl3): ¤ 0.89 (t, J = 7.3 Hz, 3H),
0.96 (t, J = 7.3 Hz, 3H), 1.37 (sext, J = 7.6 Hz, 2H), 1.62 (sext,
J = 7.5 Hz, 2H), 2.03 (t, J = 7.9 Hz, 2H), 2.24 (t, J = 7.6 Hz,
2H), 3.70 (s, 2H), 7.14 (dt, J = 8.4, 2.1 Hz, 2H), 7.27 (dt,
J = 8.6, 2.3 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.4,
14.1, 21.3, 21.7, 31.6, 32.7, 41.2, 111.7, 119.4, 128.7, 130.0,
132.6, 136.3, 157.2. IR (neat): 2963, 2932, 2872, 2341, 2208,
1624, 1491, 1466, 1408, 1381, 1092, 1016, 912, 800,
735 cm¹1. Anal. Calcd for C16H20ClN: C, 73.41, H, 7.70%.
Found: C, 73.62, H, 7.94%.
(E)-2-Propylhex-2-enenitrile (4): A colorless oil, Rf =
0.18 (hexane-ethyl acetate = 40:1). 1H NMR (400 MHz,
CDCl3): ¤ 0.94 (t, J = 7.4 Hz, 3H), 0.95 (t, J = 7.4 Hz, 3H),
1.46 (sext, J = 7.4 Hz, 2H), 1.58 (sext, J = 7.4 Hz, 2H), 2.17
(quint, J = 7.5 Hz, 4H), 6.35 (t, J = 7.6 Hz, 1H); 13C NMR
(101 MHz, CDCl3): ¤ 13.5, 13.8, 21.4, 21.9, 30.4, 30.5, 114.8,
120.1, 147.9. IR (neat): 2963, 2934, 2874, 2216, 1634, 1460,
1381, 1067, 908 cm¹1. HRMS (EI) Calcd for C9H15N: M+,
137.1204. Found: m/z 137.1209.
Carbocyanation of Alkynes with Arylacetonitriles.
General procedure: In a dry box, to a stirred mixture of an
arylacetonitrile (1.00 mmol), an alkyne (1.00 mmol), and
tetradecane (internal standard, 99 mg, 0.50 mmol) placed in a
vial were added a solution of Ni(cod)2 (5.5 mg, 20 ¯mol), 2-
Mes-C6H4-PCy2 (15.7 mg, 40 ¯mol) and a 1.0 M solution of
AlMe2Cl in hexane (80 ¯L, 80 ¯mol) in toluene (1.0 mL)
placed in a vial. The vial was taken out from the dry box and
stirred at 35 °C for the time specified in Tables 3 and 4. The
resulting mixture was filtered through a Florisil pad, concen-
trated in vacuo, and purified by flash column chromatography
on silica gel to give the corresponding carbocyanation products
in yields listed in Tables 3 and 4. Regio- and/or stereoisomers
were separated by preparative GPC or HPLC and characterized
by spectrometry.
(Z)-3-Benzyl-2-propylhex-2-enenitrile (3da): A colorless
oil, Rf = 0.41 (hexane-ethyl acetate = 10:1). 1H NMR (400
MHz, CDCl3): ¤ 0.88 (t, J = 7.3 Hz, 3H), 0.97 (t, J = 7.3 Hz,
3H), 1.38 (sext, J = 7.6 Hz, 2H), 1.63 (sext, J = 7.5 Hz, 2H),
2.04 (t, J = 8.0 Hz, 2H), 2.24 (t, J = 7.6 Hz, 2H), 3.74 (s, 2H),
7.19-7.27 (m, 3H), 7.30 (tt, J = 7.1, 1.5 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 13.5, 14.1, 21.3, 21.8, 31.6, 32.7, 42.0,
111.2, 119.6, 126.7, 128.6, 128.7, 137.8, 157.9. IR (neat):
2963, 2932, 2872, 2206, 1624, 1603, 1495, 1454, 1381, 1086,
1030, 737, 702 cm¹1. Anal. Calcd for C16H21N: C, 84.53; H,
9.31%. Found: C, 84.46; H, 9.39%.
(Z)-3-(Biphenyl-4-ylmethyl)-2-propylhex-2-enenitrile (3ea):
A colorless oil, Rf = 0.41 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.91 (t, J = 7.3 Hz, 3H), 0.98
(t, J = 7.3 Hz, 3H), 1.42 (sext, J = 7.6 Hz, 2H), 1.65 (sext,
J = 7.5 Hz, 2H), 2.09 (t, J = 8.0 Hz, 2H), 2.26 (t, J = 7.6 Hz,
2H), 3.78 (s, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.34 (tt, J = 7.4,
1.5 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.53 (dt, J = 8.4, 2.0 Hz,
2H), 7.56-7.60 (m, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.5,
14.1, 21.3, 21.7, 31.6, 32.7, 41.6, 111.3, 119.6, 126.9, 127.2,
(Z)-3-[(4-Methoxyphenyl)methyl]-2-propylhex-2-enenitrile
(3ga):
A colorless oil, Rf = 0.13 (hexane-ethyl acetate =
1
10:1). H NMR (400 MHz, CDCl3): ¤ 0.88 (t, J = 7.3 Hz, 3H),
0.96 (t, J = 7.4 Hz, 3H), 1.37 (sext, J = 7.6 Hz, 2H), 1.62 (sext,
J = 7.5 Hz, 2H), 2.03 (t, J = 8.0 Hz, 2H), 2.23 (t, J = 7.6 Hz,
2H), 3.67 (s, 2H), 3.79 (s, 3H), 6.83 (dt, J = 8.8, 2.6 Hz, 2H),
7.13 (dt, J = 8.8, 2.6 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤
13.4, 14.0, 21.2, 21.6, 31.5, 32.5, 41.0, 55.1, 110.7, 113.9,
119.6, 129.6, 129.7, 158.2, 158.3. IR (neat): 2963, 2934, 2872,
2835, 2361, 2343, 2206, 1611, 1512, 1464, 1441, 1302, 1250,
1178, 1115, 1036, 816 cm¹1. Anal. Calcd for C17H23NO: C,
79.33; H, 9.01%. Found: C, 79.50; H, 9.03%.
(Z)-3-[(3,4-Methylenedioxyphenyl)methyl]-2-propylhex-
2-enenitrile (3ha): A colorless oil, Rf = 0.39 (hexane-ethyl
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 0.89 (t, J =
7.4 Hz, 3H), 0.97 (t, J = 7.3 Hz, 3H), 1.37 (sext, J = 7.6 Hz,
2H), 1.62 (sext, J = 7.5 Hz, 2H), 2.04 (t, J = 7.9 Hz, 2H), 2.23
(t, J = 7.7 Hz, 2H), 3.65 (s, 2H), 5.94 (s, 2H), 6.66 (dd,
J = 7.9, 1.6 Hz, 1H), 6.69 (d, J = 1.8 Hz, 1H), 6.74 (d, J =
7.9 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤ 13.4, 14.1,
21.3, 21.7, 31.5, 32.5, 41.5, 100.9, 108.2, 108.9, 111.1,
119.5, 121.7, 131.4, 146.3, 147.8, 157.9. IR (neat): 2963,
2932, 2874, 2206, 1504, 1489, 1443, 1246, 1186, 1097, 1040,
928, 810, 773 cm¹1. Anal. Calcd for C17H21NO2: C, 75.25; H,
7.80%. Found: C, 75.45; H, 7.89%.
(Z)-3-[(2-Methoxycarbonylphenyl)methyl]-2-propylhex-
2-enenitrile (3ia):
A yellow oil, Rf = 0.31 (hexane-ethyl
acetate = 10:1). 1H NMR (400 MHz, CDCl3): ¤ 0.84 (t, J = 7.6
Hz, 3H), 0.98 (t, J = 7.3 Hz, 3H), 1.33 (sext, J = 7.6 Hz, 2H),
1.64 (sext, J = 7.5 Hz, 2H), 1.99 (t, J = 8.0 Hz, 2H), 2.26 (t,
J = 7.6 Hz, 2H), 3.91 (s, 3H), 4.22 (s, 2H), 7.22-7.33 (m, 2H),
7.44 (td, J = 7.6, 1.5 Hz, 1H), 7.88 (dd, J = 7.8, 1.4 Hz, 1H);
13C NMR (101 MHz, CDCl3): ¤ 13.5, 14.1, 21.5, 21.8, 31.7,
33.0, 38.8, 52.2, 112.0, 119.5, 126.7, 130.1, 130.2, 130.8,
132.1, 139.0, 157.8, 168.1. IR (neat): 2963, 2874, 2206, 1720,
1435, 1265, 1192, 1109, 1078, 739 cm¹1. Anal. Calcd for
C18H23NO2: C, 75.76; H, 8.12%. Found: C, 75.82; H, 8.27%.
(Z)-3-[(2-Methoxyphenyl)methyl]-2-propylhex-2-enenitrile
(3ja):
A colorless oil, Rf = 0.30 (hexane-ethyl acetate =
1
10:1). H NMR (400 MHz, CDCl3): ¤ 0.87 (t, J = 7.4 Hz, 3H),
0.96 (t, J = 7.3 Hz, 3H), 1.37 (sext, J = 7.6 Hz, 2H), 1.61 (sext,
J = 7.5 Hz, 2H), 2.02 (t, J = 8.0 Hz, 2H), 2.23 (t, J = 7.5 Hz,
2H), 3.76 (s, 2H), 3.83 (s, 3H), 6.85 (d, J = 8.2 Hz, 1H), 6.89

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Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
(td, J = 7.5, 1.1 Hz, 1H), 7.13 (dd, J = 7.3, 1.6 Hz, 1H), 7.22
(td, J = 8.1, 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤ 13.3,
14.1, 21.4, 21.7, 31.6, 32.6, 35.8, 55.1, 110.2, 110.9, 119.6,
120.4, 126.2, 127.9, 129.9, 157.5, 157.8. IR (neat): 2963, 2934,
2872, 2837, 2361, 2343, 2206, 1624, 1599, 1587, 1493, 1464,
1439, 1290, 1246, 1123, 1051, 1030, 754 cm¹1. Anal. Calcd for
C17H23NO: C, 79.33; H, 9.01%. Found: C, 79.21; H, 9.18%.
(Z)-2-Propyl-3-[(2,4,6-trimethylphenyl)methyl]hex-2-ene-
J = 7.7 Hz, 1H), 7.37 (d, J = 8.1 Hz, 1H), 7.65 (d, J = 7.9 Hz,
1H), 8.07 (br s, 1H); 13C NMR (101 MHz, CDCl3): ¤ 13.7,
14.3, 21.6, 21.9, 31.8, 32.1, 32.9, 110.1, 111.0, 112.3, 118.8,
119.5, 119.6, 122.0, 122.4, 127.2, 136.0, 158.4. IR (neat):
3414, 2963, 2932, 2872, 2206, 1620, 1456, 1433, 1339, 1232,
1094, 1011, 910, 737, 648 cm¹1. Anal. Calcd for C18H22N2: C,
81.16; H, 8.32%. Found: C, 81.07; H, 8.33%.
(Z)-3-(Diphenylmethyl)-2-propylhex-2-enenitrile (3pa):
nitrile (3ka):
A colorless oil, Rf = 0.37 (hexane-ethyl
A colorless oil, Rf = 0.37 (hexane-ethyl acetate = 10:1).
1
acetate = 10:1). H NMR (400 MHz, CDCl3): ¤ 0.81 (t, J =
7.3 Hz, 3H), 0.97 (t, J = 7.3 Hz, 3H), 1.22 (sext, J = 7.8 Hz,
2H), 1.62 (sext, J = 7.5 Hz, 2H), 1.86 (t, J = 8.2 Hz, 2H), 2.22
(t, J = 7.7 Hz, 2H), 2.26 (s, 3H), 2.27 (s, 6H), 3.82 (s, 2H), 6.84
(s, 2H); 13C NMR (101 MHz, CDCl3): ¤ 13.6, 14.3, 20.4, 20.8,
21.6, 22.1, 31.7, 32.4, 36.4, 110.0, 119.2, 129.2, 131.3, 136.1,
137.3, 157.5. IR (neat): 2963, 2932, 2872, 2206, 1614, 1456,
1379, 912, 851, 735 cm¹1. Anal. Calcd for C19H27N: C, 84.70;
H, 10.10%. Found: C, 84.92; H, 10.23%.
1H NMR (400 MHz, CDCl3): ¤ 0.59-0.73 (m, 5H), 1.01 (t,
J = 7.3 Hz, 3H), 1.68 (sext, J = 7.5 Hz, 2H), 2.20 (t, J =
8.0 Hz, 2H), 2.28 (t, J = 7.7 Hz, 2H), 5.70 (s, 1H), 7.16 (d,
J = 5.1 Hz, 4H), 7.23-7.35 (m, 6H); 13C NMR (101 MHz,
CDCl3): ¤ 13.6, 14.6, 21.6, 22.7, 32.1, 33.5, 57.4, 113.1, 118.9,
126.9, 128.4, 129.1, 140.7, 159.5. IR (neat): 2963, 2932, 2872,
2206, 1601, 1495, 1454, 1379, 1115, 1078, 1032, 910, 733,
698 cm¹1. Anal. Calcd for C22H25N: C, 87.08; H, 8.30%.
Found: C, 86.85; H, 8.43%.
(Z)-3-(2-Naphthylmethyl)-2-propylhex-2-enenitrile (3la):
A colorless oil, Rf = 0.42 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.88 (t, J = 7.4 Hz, 3H), 0.99
(t, J = 7.3 Hz, 3H), 1.41 (sext, J = 7.6 Hz, 2H), 1.66 (sext,
J = 7.5 Hz, 2H), 2.07 (t, J = 8.0 Hz, 2H), 2.28 (t, J = 7.5 Hz,
2H), 3.91 (s, 2H), 7.35 (dd, J = 8.4, 1.8 Hz, 1H), 7.42-7.51 (m,
2H), 7.64 (s, 1H), 7.71-7.86 (m, 3H); 13C NMR (101 MHz,
CDCl3): ¤ 13.4, 14.0, 21.3, 21.7, 31.6, 32.6, 42.1, 111.4, 119.6,
125.6, 126.1, 126.8, 127.2, 127.5, 127.6, 128.3, 132.3, 133.4,
135.3, 157.7. IR (neat): 2963, 2932, 2872, 2206, 1624, 1601,
1508, 1458, 818, 756 cm¹1. Anal. Calcd for C20H23N: C, 86.59;
H, 8.36%. Found: C, 86.50; H, 8.58%.
(Z)-2-Propyl-3-(3-thienylmethyl)hex-2-enenitrile (3ma):
A colorless oil, Rf = 0.46 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.90 (t, J = 7.4 Hz, 3H), 0.96
(t, J = 7.3 Hz, 3H), 1.38 (sext, J = 7.5 Hz, 2H), 1.61 (sext,
J = 7.4 Hz, 2H), 2.08 (t, J = 8.0 Hz, 2H), 2.23 (t, J = 7.7 Hz,
2H), 3.73 (s, 2H), 6.96 (d, J = 4.9 Hz, 1H), 7.02 (dd, J = 1.8,
0.9 Hz, 1H), 7.24-7.30 (m, 1H); 13C NMR (101 MHz, CDCl3):
¤ 13.3, 14.0, 21.2, 21.6, 31.4, 32.8, 36.6, 110.9, 119.2, 121.7,
125.8, 127.9, 137.7, 157.4. IR (neat): 2963, 2932, 2872, 2206,
1624, 1464, 1381, 1082, 787, 745 cm¹1. Anal. Calcd for
C14H19NS: C, 72.05; H, 8.21%. Found: C, 72.29; H, 8.11%.
(Z)-2-Propyl-3-(pyrrol-2-ylmethyl)hex-2-enenitrile (3na):
A slightly brown oil, Rf = 0.23 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.91 (t, J = 7.3 Hz, 3H), 0.95
(t, J = 7.4 Hz, 3H), 1.40 (sext, J = 7.6 Hz, 2H), 1.60 (sext,
J = 7.5 Hz, 2H), 2.13 (t, J = 7.9 Hz, 2H), 2.20 (t, J = 7.7 Hz,
2H), 3.69 (s, 2H), 5.96-6.02 (m, 1H), 6.12 (dd, J = 5.9, 2.7 Hz,
1H), 6.70 (ddd, J = 2.7, 1.5, 1.3 Hz, 1H), 8.14 (br s, 1H);
13C NMR (101 MHz, CDCl3): ¤ 13.5, 14.1, 21.2, 21.7, 31.5,
33.2, 34.4, 107.1, 108.4, 110.6, 117.5, 119.8, 127.5, 157.7.
IR (neat): 3373, 2963, 2932, 2872, 2208, 1624, 1566, 1466,
1381, 1121, 1094, 1026, 912, 883, 795, 716 cm¹1. Anal. Calcd
for C14H20N2: C, 77.73; H, 9.32%. Found: C, 77.87; H, 9.07%.
(Z)-3-(Indol-3-ylmethyl)-2-propylhex-2-enenitrile (3oa):
A slightly brown oil, Rf = 0.24 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.90 (t, J = 7.3 Hz, 3H), 0.98
(t, J = 7.3 Hz, 3H), 1.43 (sext, J = 7.6 Hz, 2H), 1.65 (sext,
J = 7.4 Hz, 2H), 2.12 (t, J = 7.9 Hz, 2H), 2.26 (t, J = 7.6 Hz,
2H), 3.89 (s, 2H), 7.05 (s, 1H), 7.14 (t, J = 7.5 Hz, 1H), 7.21 (t,
(Z)-3-Benzyl-4-trimethylsilyl-2-[(trimethylsilyl)methyl]-
but-2-enenitrile (3db): A colorless oil, Rf = 0.25 (hexane-
ethyl acetate = 20:1). H NMR (400 MHz, CDCl3): ¤ 0.11 (s,
9H), 0.12 (s, 9H), 1.61 (s, 2H), 1.64 (s, 2H), 3.69 (s, 2H), 7.19-
7.26 (m, 3H), 7.31 (tt, J = 7.1, 1.3 Hz, 2H); 13C NMR (101
MHz, CDCl3): ¤ ¹0.9, ¹0.2, 21.4, 24.2, 43.7, 103.4, 121.0,
126.5, 128.4, 128.6, 138.4, 153.9. IR (neat): 3063, 3028, 2955,
1
2899, 2203, 1603, 1495, 1454, 1437, 1418, 1250, 1219, 1173,
¹1
1142, 1084, 1030, 957, 847, 762, 727, 700, 610, 552 cm
.
Anal. Calcd for C18H29NSi2: C, 68.50; H, 9.26%. Found: C,
68.73; H, 9.09%.
(E)-2,3,4-Triphenylbut-2-enenitrile [(E)-3di]: A colorless
solid, mp: 105.0-106.0 °C, Rf = 0.23 (hexane-ethyl acetate =
1
20:1). H NMR (400 MHz, CDCl3): ¤ 4.27 (s, 2H), 6.89-6.95
(m, 2H), 7.11-7.26 (m, 13H); 13C NMR (101 MHz, CDCl3): ¤
44.9, 112.8, 119.2, 126.7, 128.09, 128.14, 128.3, 128.4, 128.5,
128.7, 129.4, 133.4, 136.6, 137.5, 157.4. IR (KBr): 3439, 3057,
3028, 2915, 2218, 1966, 1954, 1896, 1881, 1821, 1805, 1755,
1599, 1575, 1493, 1454, 1441, 1431, 1219, 1184, 1107, 1069,
1030, 1001, 976, 945, 926, 910, 854, 833, 773, 750, 702, 677,
637, 600, 561, 517, 488, 461 cm¹1. Anal. Calcd for C22H17N:
C, 89.46; H, 5.80%. Found: C, 89.42; H, 5.74%.
(Z)-2,3,4-Triphenylbut-2-enenitrile [(Z)-3di]: A yellow
solid, mp: 103.5-104.3 °C, Rf = 0.15 (hexane-ethyl acetate =
1
20:1). H NMR (400 MHz, CDCl3): ¤ 3.96 (s, 2H), 6.95 (d,
J = 6.6 Hz, 2H), 7.11-7.22 (m, 3H), 7.32-7.51 (m, 10H);
13C NMR (101 MHz, CDCl3): ¤ 40.0, 113.8, 119.0, 126.4,
128.0, 128.2, 128.4, 128.5, 128.80, 128.83, 129.0, 129.1,
134.0, 136.9, 138.7, 157.8. IR (KBr): 3443, 3061, 3028, 2207,
1981, 1960, 1888, 1809, 1763, 1603, 1591, 1570, 1495, 1445,
1290, 1277, 1244, 1180, 1157, 1074, 1030, 999, 947, 920, 893,
¹1
791, 777, 766, 731, 708, 698, 567, 517, 490, 461, 446 cm
.
Anal. Calcd for C22H17N: C, 89.46; H, 5.80%. Found: C,
89.29; H, 5.84%. Crystallographic data have been deposited
with Cambridge Crystallographic Data Centre: Deposition
number CCDC-727199 for compound (Z)-3di. Copies of the
data can be obtained free of charge via http://www.ccdc.
cam.ac.uk/conts/retrieving.html (or from the Cambridge Crys-
tallographic Data Centre, 12, Union Road, Cambridge, CB2
1EZ, U.K.; Fax: +44 1223 336033; e-mail: deposit@ccdc.cam.
ac.uk).

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
631
(Z)-3-Methyl-2,4-diphenylbut-2-enenitrile (3dc): A col-
orless oil, Rf = 0.33 (hexane-ethyl acetate = 10:1). H NMR
2855, 2206, 1587, 1495, 1452, 1254, 1080, 1030, 843, 760,
739, 700 cm¹1. Anal. Calcd for C14H19NSi: C, 73.30; H,
8.35%. Found: C, 73.56; H, 8.37%.
1
(400 MHz, CDCl3): ¤ 1.81 (s, 3H), 3.91 (s, 2H), 7.26-7.43 (m,
10H); 13C NMR (101 MHz, CDCl3): ¤ 19.2, 44.5, 111.6, 119.0,
126.9, 128.3, 128.5, 128.70, 128.73, 129.1, 133.8, 137.3,
156.5. IR (neat): 3061, 3028, 2210, 1601, 1493, 1447, 1375,
1076, 1030, 1005, 989, 912, 767, 750, 700 cm¹1. HRMS (EI)
Calcd for C17H15N: M+, 233.1204. Found: m/z 233.1214.
(Z)-3-Benzylnon-2-enenitrile (3dm): A pale yellow oil,
1
Rf = 0.33 (hexane-ethyl acetate = 15:1). H NMR (400 MHz,
CDCl3): ¤ 0.87 (t, J = 7.0 Hz, 3H), 1.20-1.48 (m, 8H), 2.08 (td,
J = 7.7, 1.3 Hz, 2H), 3.74 (s, 2H), 5.21 (s, 1H), 7.20-7.25 (m,
5H); 13C NMR (101 MHz, CDCl3): ¤ 14.1, 22.6, 27.1, 28.8,
31.5, 35.5, 41.1, 95.4, 117.4, 126.8, 128.59, 128.64, 136.9,
167.3. IR (neat): 3086, 3063, 3028, 2955, 2930, 2857, 2216,
1624, 1601, 1495, 1454, 1379, 1076, 1030, 827, 737, 700
cm¹1. Anal. Calcd for C16H21N: C, 84.53; H, 9.31%. Found: C,
84.79; H, 9.27%.
(E)-2-Methyl-3,4-diphenylbut-2-enenitrile (3¤dc):
A
colorless oil, Rf = 0.33 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 1.85 (s, 3H), 4.04 (s, 2H),
6.90-6.96 (m, 2H), 7.02-7.07 (m, 2H), 7.14-7.23 (m, 3H),
7.26-7.33 (m, 3H); 13C NMR (101 MHz, CDCl3): ¤ 17.9, 44.5,
106.5, 119.9, 126.5, 127.6, 128.1, 128.2, 128.3, 128.7, 136.8,
137.4, 157.1. IR (neat): 3061, 3028, 2924, 2855, 2361, 2343,
2210, 1601, 1493, 1443, 1375, 1076, 1030, 1005, 912, 779,
766, 735, 702, 565 cm¹1. HRMS (EI) Calcd for C17H15N: M+,
233.1204. Found: m/z 233.1195.
(Z)-2-(2-Phenylethynylidene)octanenitrile (3¤dm):
A
colorless oil, Rf = 0.38 (hexane-ethyl acetate = 15:1).
1H NMR (400 MHz, CDCl3): ¤ 0.89 (t, J = 6.9 Hz, 3H),
1.23-1.37 (m, 6H), 1.51-1.62 (m, 2H), 2.24 (t, J = 7.5 Hz,
2H), 3.69 (d, J = 7.7 Hz, 2H), 6.26 (t, J = 7.7 Hz, 1H), 7.17-
7.27 (m, 3H), 7.32 (t, J = 7.4 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 14.1, 22.6, 28.1, 28.4, 31.5, 34.3, 37.8, 115.3, 117.6,
126.7, 128.3, 128.7, 137.7, 145.2. IR (neat): 3030, 2955, 2928,
2859, 2214, 1603, 1495, 1454, 1435, 1379, 1261, 1105, 1076,
1030, 797, 739, 698, 569 cm¹1. HRMS (EI) Calcd for C16H21N:
M+, 227.1674. Found: m/z 227.1676.
(Z)-2-Ethyl-3-methyl-4-phenylbut-2-enenitrile (3dj):
A
colorless oil, Rf = 0.31 (hexane-ethyl acetate = 10:1). 1H NMR
(400 MHz, CDCl3): ¤ 1.17 (t, J = 7.6 Hz, 3H), 1.73 (s, 3H),
2.28 (q, J = 7.6 Hz, 2H), 3.71 (s, 2H), 7.20-7.34 (m, 5H);
13C NMR (101 MHz, CDCl3): ¤ 12.8, 17.6, 23.4, 44.4, 112.0,
119.3, 126.8, 128.6, 128.7, 137.7, 153.3. IR (neat): 3028, 2974,
2936, 2876, 2208, 1630, 1603, 1495, 1454, 1377, 752, 704
cm¹1. HRMS (EI) Calcd for C13H15N: M+, 185.1204. Found:
m/z 185.1199.
(Z)-3-Cyclohexyl-4-phenylbut-2-enenitrile (3dn):
A
colorless oil, Rf = 0.16 (hexane-ethyl acetate = 20:1).
1H NMR (400 MHz, CDCl3): ¤ 1.00-1.30 (m, 5H), 1.62-1.80
(m, 5H), 1.98 (t, J = 11.2 Hz, 1H), 3.78 (s, 2H), 5.24 (s, 1H),
7.19-7.25 (m, 3H), 7.31 (tt, J = 7.1, 1.5 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 26.0, 26.3, 32.1, 40.4, 43.3, 94.6, 117.7,
126.7, 128.6, 136.9, 171.8. IR (neat): 3061, 3028, 2930, 2853,
2216, 1618, 1601, 1584, 1495, 1451, 1300, 1269, 1182, 1144,
1076, 1030, 980, 893, 827, 816, 775, 737, 700 cm¹1. Anal.
Calcd for C16H19N: C, 85.28; H, 8.50%. Found: C, 85.38; H,
8.61%.
(Z)-3-Benzyl-2-methylpent-2-enenitrile (3¤dj): A color-
less oil, Rf = 0.31 (hexane-ethyl acetate = 10:1). 1H NMR
(400 MHz, CDCl3): ¤ 0.95 (t, J = 7.7 Hz, 3H), 1.96 (s, 3H),
2.10 (q, J = 7.6 Hz, 2H), 3.74 (s, 2H), 7.20-7.34 (m, 5H);
13C NMR (101 MHz, CDCl3): ¤ 12.0, 16.1, 24.1, 41.7, 104.5,
120.2, 126.7, 128.5, 128.7, 137.5, 159.5. IR (neat): 3028, 2966,
2934, 2874, 2361, 2341, 2208, 1603, 1489, 1454, 1379, 912,
735, 702 cm¹1. HRMS (EI) Calcd for C13H15N: M+, 185.1204.
Found: m/z 185.1196.
(Z)-2-Cyclohexyl-4-phenylbut-2-enenitrile (3¤dn):
A
(Z)-2-tert-Butyl-3-methyl-4-phenylbut-2-enenitrile (3dk):
A colorless oil, Rf = 0.43 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 1.33 (s, 9H), 1.91 (s, 3H),
3.76 (s, 2H), 7.19-7.27 (m, 3H), 7.31 (tt, J = 7.1, 1.6 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ 19.8, 30.6, 33.6, 46.5, 119.3,
120.4, 126.7, 128.5, 128.6, 137.8, 154.4. IR (neat): 2970, 2206,
1601, 1495, 1454, 1367, 914, 735, 700, 428 cm¹1. Anal. Calcd
for C15H19N: C, 84.46; H, 8.98%. Found: C, 84.55; H, 9.03%.
(E)-3-Methyl-4-phenyl-2-trimethylsilylbut-2-enenitrile
colorless oil, Rf = 0.23 (hexane-ethyl acetate = 20:1).
1H NMR (400 MHz, CDCl3): ¤ 1.10-1.42 (m, 5H), 1.69 (d,
J = 5.3 Hz, 1H), 1.82 (t, J = 11.8 Hz, 4H), 2.15 (td, J = 11.2,
3.0 Hz, 1H), 3.69 (d, J = 7.7 Hz, 2H), 6.26 (td, J = 7.7, 0.9 Hz,
1H), 7.19 (d, J = 7.3 Hz, 2H), 7.24 (tt, J = 7.5, 2.2 Hz, 1H),
7.32 (t, J = 7.1 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤ 25.6,
26.0, 31.8, 37.7, 42.6, 117.2, 121.3, 126.6, 128.3, 128.6, 137.8,
143.1. IR (neat): 3063, 3028, 2928, 2853, 2214, 1603, 1495,
1451, 1350, 1076, 1030, 990, 936, 891, 741, 689, 646, 573,
513 cm¹1. HRMS (EI) Calcd for C16H19N: M+, 225.1517.
Found: m/z 225.1524.
(3dl):
A colorless oil, Rf = 0.42 (hexane-ethyl acetate =
10:1). 1H NMR (400 MHz, CDCl3): ¤ 0.31 (s, 9H), 1.88 (s, 3H),
3.82 (s, 2H), 7.20-7.28 (m, 3H), 7.32 (tt, J = 7.2, 1.6 Hz, 2H);
13C NMR (101 MHz, CDCl3): ¤ ¹0.4, 22.1, 46.7, 110.0, 120.4,
126.8, 128.7, 128.8, 137.5, 171.5. IR (neat): 3029, 2959, 2901,
2193, 1582, 1495, 1454, 1375, 1254, 1028, 880, 845, 762, 745,
700, 633, 559 cm¹1. Anal. Calcd for C14H19NSi: C, 73.30; H,
8.35%. Found: C, 73.56; H, 8.37%.
(E)-3-Benzyl-4,4-dimethylpent-2-enenitrile (3do):
A
colorless oil, Rf = 0.31 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 1.07 (s, 9H), 3.87 (s, 2H),
5.52 (s, 1H), 7.19-7.25 (m, 3H), 7.27-7.33 (m, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 29.5, 38.2, 38.3, 96.7, 117.8, 126.4,
128.0, 128.4, 137.3, 173.8. IR (neat): 3063, 3028, 2969, 2870,
2216, 1609, 1495, 1479, 1468, 1454, 1397, 1366, 1260, 1215,
1196, 1096, 1076, 1030, 978, 926, 824, 764, 719, 696,
671 cm¹1. Anal. Calcd for C14H17N: C, 84.37; H, 8.60%.
Found: C, 84.38; H, 8.56%.
(E)-2-Methyl-4-phenyl-3-trimethylsilylbut-2-enenitrile
(3¤dl): A colorless oil, Rf = 0.47 (hexane-ethyl acetate =
10:1). 1H NMR (400 MHz, CDCl3): ¤ 0.08 (s, 9H), 2.17 (s, 3H),
3.87 (s, 2H), 7.11 (d, J = 7.0 Hz, 2H), 7.17-7.35 (m, 3H);
13C NMR (101 MHz, CDCl3): ¤ ¹0.4, 20.5, 43.0, 118.8, 119.3,
126.5, 128.4, 128.8, 137.9, 159.3. IR (neat): 3028, 2955, 2901,
Carbocyanation of Alkynes with Functionzalized Aceto-
nitriles. General procedure: In a dry box, to a solution of

632
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010) BCSJ AWARD ARTICLE
Ni(cod)2 (14 mg, 50 ¯mol) and a ligand (0.10 mmol) in toluene
(1.0 mL) placed in a vial were sequentially added a substituted
acetonitrile (1.00 mmol), BPh3 (48 mg, 0.20 mmol), an alkyne
(2.0 mmol), and dodecane (internal standard, 85 mg, 0.50
mmol). The vial was taken out from the dry box and heated
at 80 °C for the time specified Table 5. The resulting mixture
was filtered through a silica gel pad, concentrated in vacuo, and
purified by flash column chromatography on silica gel to give
the corresponding carbocyanation products in yields listed in
Table 5. Regio- and/or stereoisomers were separated by
preparative GPC or HPLC and characterized by spectrometry.
(Z)-3-(Phthalimidomethyl)-2-propylhex-2-enenitrile (3qa):
A colorless solid, mp: 38.1-38.7 °C, Rf = 0.12 (hexane-ethyl
MHz, CDCl3): ¤ 17.5, 30.5, 34.1, 45.2, 117.5, 122.3, 123.4,
131.6, 134.1, 148.2, 167.6. IR (KBr): 2976, 2206, 1774, 1717,
1423, 1398, 1348, 1119, 924, 729, 712 cm¹1. Anal. Calcd for
C17H18N2O2: C, 72.32; H, 6.43%. Found: C, 72.59; H, 6.51%.
(Z)-2-Propyl-3-(tetrahydro-2H-pyran-2-yloxymethyl)hex-
2-enenitrile (3ra): A colorless oil, Rf = 0.15 (hexane-ethyl
acetate = 15:1). 1H NMR (400 MHz, CDCl3): ¤ 0.96 (t, J = 7.1
Hz, 3H), 0.97 (t, J = 7.0 Hz, 3H), 1.41-1.67 (m, 8H), 1.69-
1.89 (m, 2H), 2.21-2.32 (m, 4H), 3.51-3.61 (m, 1H), 3.82-3.92
(m, 1H), 4.26 (d, J = 12.3 Hz, 1H), 4.46 (d, J = 12.3 Hz, 1H),
4.64 (t, J = 3.4 Hz, 1H); 13C NMR (101 MHz, CDCl3): ¤ 13.6,
14.3, 19.4, 21.4, 21.6, 25.4, 30.5, 31.7, 31.8, 62.3, 68.4, 98.5,
112.3, 118.1, 154.9. IR (neat): 2961, 2872, 2210, 1630, 1464,
1456, 1383, 1350, 1261, 1202, 1182, 1157, 1119, 1078, 1057,
1034, 972, 907, 870, 816 cm¹1. Anal. Calcd for C15H25NO2: C,
71.67; H, 10.02%. Found: C, 71.62; H, 10.23%.
1
acetate = 7:1). H NMR (400 MHz, CDCl3): ¤ 0.91 (t, J = 7.3
Hz, 3H), 0.97 (t, J = 7.3 Hz, 3H), 1.47 (sext, J = 7.6 Hz, 2H),
1.63 (sext, J = 7.5 Hz, 2H), 2.08 (t, J = 8.0 Hz, 2H), 2.25 (t,
J = 7.6 Hz, 2H), 4.62 (s, 2H), 7.74 (dd, J = 5.5, 3.1 Hz, 2H),
7.87 (dd, J = 5.5, 3.1 Hz, 2H); 13C NMR (101 MHz, CDCl3): ¤
13.6, 14.2, 21.51, 21.55, 31.6, 32.1, 41.7, 113.8, 117.8, 123.4,
(Z)-2-Propyl-3-[(trimethylsilyl)methyl]hex-2-enenitrile
(3sa): A pale yellow oil, Rf = 0.18 (hexane-ethyl acetate =
50:1). 1H NMR (400 MHz, CDCl3): ¤ 0.11 (s, 9H), 0.94 (t,
J = 7.3 Hz, 3H), 0.95 (t, J = 7.3 Hz, 3H), 1.44 (sext, J =
7.6 Hz, 2H), 1.56 (sext, J = 7.5 Hz, 2H), 2.02 (s, 2H), 2.08 (t,
J = 7.8 Hz, 2H), 2.16 (t, J = 7.5 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ ¹0.6, 13.6, 14.2, 21.6, 22.3, 28.8, 31.4, 35.7, 105.7,
120.4, 159.1. IR (neat): 2961, 2874, 2203, 1611, 1464, 1421,
1379, 1250, 1148, 1078, 853, 766, 694 cm¹1. Anal. Calcd for
C13H25NSi: C, 69.88; H, 11.28%. Found: C, 70.18; H, 11.17%.
Carbocyanation of 2a with (S)-1t (eq 3). In a dry box, to a
solution of Ni(cod)2 (55 mg, 0.2 mmol) and 2-(2,4,6-i-Pr3-
C6H2)-C6H4-PCy2 (191 mg, 0.4 mmol) in toluene (1.0 mL)
placed in a vial were added (S)-1t (131 mg, 1.00 mmol), a 1.0 M
solution of AlMe2Cl in hexane (0.20 mL, 0.20 mmol), 2a
(0.55 g, 5.0 mmol), and tridecane (internal standard, 92 mg,
0.50 mmol) sequentially. The vial was taken out from the dry
box and heated at 80 °C for 0.5 h. GC analysis of the mixture
showed the formation of hydrocyanation product 4, styrene 6,
and hydrocinnamonitrile 7 in 35%, 44%, and 3% yield,
respectively. The mixture was filtered through a silica gel pad
and concentrated in vacuo. The residue was purified by flash
column chromatography on silica gel followed by prepara-
tive HPLC to give (S)-(Z)-3-(1-phenylethyl)-2-propylhex-2-
enenitrile [(S)-3ta] (54 mg, 22%) and (S)-1t (17 mg, 13%). (S)-
3ta: A colorless oil, Rf = 0.27 (hexane-ethyl acetate = 10:1).
1H NMR (400 MHz, CDCl3): ¤ 0.73-0.91 (m, 4H), 0.96 (t,
J = 7.4 Hz, 3H), 1.09-1.27 (m, 1H), 1.47 (d, J = 7.1 Hz, 3H),
1.64 (sext, J = 7.5 Hz, 2H), 1.91 (t, J = 8.2 Hz, 2H), 2.18 (t,
J = 7.6 Hz, 2H), 4.46 (q, J = 7.1 Hz, 1H), 7.20-7.35 (m, 5H);
13C NMR (101 MHz, CDCl3): ¤ 13.5, 14.6, 17.1, 21.5, 23.1,
30.9, 31.7, 45.6, 110.2, 119.3, 126.8, 127.4, 128.3, 141.6,
162.7. IR (neat): 2964, 2934, 2874, 2206, 1601, 1495, 1450,
1379, 1123, 1090, 1022, 912, 735, 700 cm¹1. Anal. Calcd for
C17H23N: C, 84.59; H, 9.60%. Found: C, 84.78; H, 9.59%.
Ee was determined by HPLC analysis on a Daicel Chiralcel
OB-H column with hexane, flow rate: 0.5 mL min¹1, detection
by UV of 254 nm. Retention times: 14.5 min [(S)-enantiomer],
131.7, 134.1, 151.2, 167.6. IR (KBr): 2964, 2934, 2874, 2212,
¹1
1773, 1717, 1466, 1425, 1396, 1350, 953, 926, 712, 530 cm
.
Anal. Calcd for C18H20N2O2: C, 72.95; H, 6.80%. Found: C,
72.78; H, 6.83%.
(Z)-3-Methyl-2-phenyl-4-phthalimidobut-2-enenitrile [(Z)-
3qc]:
A colorless solid, mp: 104.1-104.8 °C, Rf = 0.13
1
(hexane-ethyl acetate = 4:1). H NMR (400 MHz, CDCl3): ¤
1.84 (s, 3H), 4.81 (s, 2H), 7.31-7.43 (m, 5H), 7.77 (dd, J = 5.5,
2.9 Hz, 2H), 7.91 (dd, J = 5.4, 3.0 Hz, 2H); 13C NMR
(101 MHz, CDCl3): ¤ 17.6, 43.2, 113.4, 117.3, 123.5, 128.6,
128.7, 128.9, 131.7, 133.2, 134.2, 150.3, 167.6. IR (KBr):
2214, 1773, 1713, 1418, 1396, 1348, 930, 766, 729, 714,
700 cm¹1. Anal. Calcd for C19H14N2O2: C, 75.48; H, 4.67%.
Found: C, 75.45; H, 4.78%.
(E)-3-Methyl-2-phenyl-4-phthalimidobut-2-enenitrile [(E)-
3qc]:
A colorless solid, mp: 111.0-111.8 °C, Rf = 0.16
1
(hexane-ethyl acetate = 4:1). H NMR (400 MHz, CDCl3): ¤
2.15 (s, 3H), 4.45 (s, 2H), 7.32-7.38 (m, 1H), 7.39-7.49 (m,
4H), 7.74 (dd, J = 5.5, 3.1 Hz, 2H), 7.84 (dd, J = 5.5, 2.9 Hz,
2H); 13C NMR (101 MHz, CDCl3): ¤ 20.0, 40.1, 114.0, 117.8,
123.4, 128.77, 128.81, 129.0, 131.5, 132.7, 134.2, 150.5,
167.5. IR (KBr): 2208, 1776, 1713, 1427, 1396, 1340, 1317,
930, 764, 731, 712, 700, 530 cm¹1. HRMS (EI) Calcd for
C19H14N2O2: M+, 302.1055. Found: m/z 302.1054.
(Z)-2-Methyl-3-phenyl-4-phthalimidobut-2-enenitrile
(3¤qc):
A colorless solid, mp: 131.7-132.6 °C, Rf = 0.17
1
(hexane-ethyl acetate = 4:1). H NMR (400 MHz, CDCl3): ¤
1.88 (t, J = 1.4 Hz, 3H), 4.93 (q, J = 1.3 Hz, 2H), 7.11 (dt, J =
6.4, 1.5 Hz, 2H), 7.21-7.31 (m, 3H), 7.65 (dd, J = 5.7, 2.9 Hz,
2H), 7.73 (dd, J = 5.6, 3.0 Hz, 2H); 13C NMR (101 MHz,
CDCl3): ¤ 18.3, 42.8, 108.8, 118.3, 123.2, 127.6, 128.4, 128.7,
131.4, 133.9, 134.5, 151.6, 167.2. IR (KBr): 2926, 2214, 1773,
1717, 1466, 1421, 1394, 1342, 1325, 1119, 1013, 945, 727,
714, 696, 530 cm¹1. HRMS (EI) Calcd for C19H14N2O2: M+,
302.1055. Found: m/z 302.1058.
30
(Z)-2-tert-Butyl-3-methyl-4-phthalimidobut-2-enenitrile
17.2 min [(R)-enantiomer]. 41% ee. ½¡ꢀD ¹145.97 (c 1.055,
(3qk):
A colorless solid, mp: 125.4-126.1 °C, Rf = 0.18
toluene). (S)-1t: The ee was determined by HPLC analysis on
a Daicel Chiralcel OD-H column with hexane, flow rate:
0.5 mL min¹1, detection by UV of 258 nm. Retention times:
37.4 min [(S)-enantiomer], 43.8 min [(R)-enantiomer]. 80% ee.
1
(hexane-ethyl acetate = 4:1). H NMR (400 MHz, CDCl3): ¤
1.33 (s, 9H), 1.92 (s, 3H), 4.67 (s, 2H), 7.75 (dd, J = 5.5,
3.1 Hz, 2H), 7.88 (dd, J = 5.6, 3.0 Hz, 2H); 13C NMR (101

A. Yada et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
633
4
For carbocyanation of other unsaturated bonds, see: a) Y.
Ruthenium-Catalyzed Oxidation of (S)-3ta. To a solu-
tion of (S)-3ta (42 mg, 0.18 mmol) in CCl4-CH3CN-H2O
(1.0:1.0:1.5, 1.4 mL) were added NaIO4 (0.38 g, 1.6 mmol) and
RuCl3¢3H2O (2.1 mg, 7.9 ¯mol) at 0 °C, and the resulting
mixture was stirred at rt for 5 h. Water was added, and the
resulting aqueous layer was extracted with CH2Cl2. The
combined organic layers were dried over MgSO4 and concen-
trated in vacuo. The residue was purified by flash column
chromatography on silica gel to give (S)-2-phenyl-3-hexanone
[(S)-8, 14 mg, 43%] as a pale yellow oil, Rf = 0.20 (hexane-
Nishihara, Y. Inoue, M. Itazaki, K. Takagi, Org. Lett. 2005, 7,
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Hiyama, Chem. Lett. 2006, 35, 790. d) Y. Nishihara, Y. Inoue, S.
Izawa, M. Miyasaka, K. Tanemura, K. Nakajima, K. Takagi,
Tetrahedron 2006, 62, 9872. e) Y. Nakao, S. Ebata, A. Yada, T.
Hiyama, M. Ikawa, S. Ogoshi, J. Am. Chem. Soc. 2008, 130,
12874. f) M. P. Watson, E. N. Jacobsen, J. Am. Chem. Soc. 2008,
130, 12594. g) Y. Yasui, H. Kamisaki, Y. Takemoto, Org. Lett.
2008, 10, 3303. h) Y. Hirata, T. Inui, Y. Nakao, T. Hiyama, J. Am.
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Takemoto, Chem. Commun. 2009, 4275.
1
ethyl acetate = 30:1). H NMR (400 MHz, CDCl3): ¤ 0.80 (t,
J = 7.4 Hz, 3H), 1.40 (d, J = 7.0 Hz, 3H), 1.47-1.58 (m, 2H),
2.33 (t, J = 7.5 Hz, 2H), 3.75 (q, J = 7.0 Hz, 1H), 7.19-7.28
(m, 3H), 7.30-7.35 (m, 2H); 13C NMR (101 MHz, CDCl3): ¤
13.7, 17.4, 17.6, 43.0, 53.0, 126.9, 127.7, 128.7, 140.6, 210.6.
IR (neat): 3028, 2964, 2932, 2874, 1713, 1601, 1493, 1452,
1373, 1130, 1070, 1015, 762, 700 cm¹1. HRMS (EI) Calcd for
C12H16O: M+, 176.1201. Found: m/z 176.1203. Ee of the
ketone was determined by HPLC analysis on a Daicel Chiralcel
OD-H column with hexane, flow rate: 0.5 mL min¹1, detection
by UV of 254 nm. Retention times: 17.2 min [(S)-enantiomer],
5
a) J. L. Burmeister, L. M. Edwards, J. Chem. Soc. A 1971,
1663. b) A. Morvillo, A. Turco, J. Organomet. Chem. 1981, 208,
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Olmstead, P. K. Mascharak, Angew. Chem., Int. Ed. 2001, 40,
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Dalton Trans. 2007, 1993.
30
18.8 min [(R)-enantiomer]. 38% ee. ½¡ꢀD +113.51 (c 0.555,
20
toluene) [lit.9 ½¡ꢀD ¹234 (c 0.281, toluene) for 91% ee of (R)-
enantiomer].
We are grateful to Professor Masaki Shimizu for X-ray
crystallographic analysis of (Z)-3di. We are grateful to a
reviewer for fruitful suggestions concerning the reaction
mechanism. This work has been supported financially by a
Grant-in-Aid for Creative Scientific Research, Scientific Re-
search (S), Young Scientists (A), and Priority Areas “Molecular
Theory for Real Systems” from MEXT and by General Sekiyu
Research & Development Encouragement & Assistance Foun-
dation. AYacknowledges the JSPS for a predoctoral fellowship.
6
For preliminary communication, see: A. Yada, T. Yukawa,
Y. Nakao, T. Hiyama, Chem. Commun. 2009, 3931, and Ref. 2d.
a) R. Martin, S. L. Buchwald, Acc. Chem. Res. 2008, 41,
7
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2000, 65, 5334. c) S. D. Walker, T. E. Barder, J. R. Martinelli, S. L.
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K. W. Anderson, D. Zim, L. Jiang, A. Klapars, S. L. Buchwald,
J. Am. Chem. Soc. 2003, 125, 6653.
8
a) N. M. Brunkan, D. M. Brestensky, W. D. Jones, J. Am.
Supporting Information
Chem. Soc. 2004, 126, 3627. b) A. Chaumonnot, F. Lamy, S. Sabo-
Etienne, B. Donnadieu, B. Chaudret, J.-C. Barthelat, J.-C. Galland,
Organometallics 2004, 23, 3363. c) J. I. van der Vlugt, A. C.
Hewat, S. Neto, R. Sablong, A. M. Mills, M. Lutz, A. L. Spek, C.
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Ramírez, M. Muñoz-Hernández, W. D. Jones, J. J. García,
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García, W. D. Jones, J. Am. Chem. Soc. 2008, 130, 8548.
1
Copies of H and 13C NMR spectra of compounds 3aa-d3,
(E)-3ab, (E)-3af, (E)-3ah, (E)-3bb, 4, 3dc, 3¤dc, 3dj, 3¤dj,
3¤dm, 3¤dn, (E)-3qc, 3¤qc, and (S)-8. This material is available
free of charge on the web at http://www.csj.jp/journals/bcsj/.
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