Copper-Catalyzed Regioselective Allylic Cyanation of Allylic Compounds with Trimethylsilyl Cyanide

Article abstract of DOI:10.1055/s-0034-1378322

The copper-catalyzed regioselective allylic cyanation of allylic compounds with trimethylsilyl cyanide (TMSCN) is described. Copper(I) iodide (CuI), copper(I) cyanide (CuCN) and copper(II) chloride (CuCl₂) are shown to effectively catalyze the cyanation of various allylic substrates to afford the corresponding allylic cyanides in good yields and high regioselectivities. The reaction in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) reveals that the cyanation proceeds via a radical pathway.

Full text of DOI:10.1055/s-0034-1378322

PAPER
▌2747
paper
Copper-Catalyzed Regioselective Allylic Cyanation of Allylic Compounds with
Trimethylsilyl Cyanide
Copper-Catalyzed Regioselective Allylic Cyanations
Daisuke Munemori,a Hiroaki Tsuji,a Kenta Uchida,a Tomoaki Suzuki,b Kazuki Isa,b Maki Minakawa,b
Motoi Kawatsura*b
a
Department of Chemistry, College of Humanities & Sciences, Nihon University, Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan
b
Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan
Fax +81(3)53179740; E-mail: kawatsur@chs.nihon-u.ac.jp
Received: 25.04.2014; Accepted after revision: 23.05.2014
tive copper catalyst4,5 for the allylic cyanation reaction
Abstract: The copper-catalyzed regioselective allylic cyanation of
was performed using various copper salts. In the event,
allylic compounds with trimethylsilyl cyanide (TMSCN) is de-
several copper(I) salts were found to catalyze the desired
scribed. Copper(I) iodide (CuI), copper(I) cyanide (CuCN) and cop-
per(II) chloride (CuCl2) are shown to effectively catalyze the
cyanation of various allylic substrates to afford the corresponding
allylic cyanides in good yields and high regioselectivities. The reac-
Table 1 Copper-Catalyzed Cyanation of Allylic Compounds
tion in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free
radical (TEMPO) reveals that the cyanation proceeds via a radical
pathway.
Ph
1a X = Cl
1b X = Br
X
Ph
CN
1c X = OCO2Me
1d X = OAc
4
Key words: copper, catalysis, regioselectivity, radical reaction, ni-
catalyst
60 °C
triles
+
Me3SiCN
and/or
X
3 (2 equiv)
CN
Ph
2a X = OCO2Me
The transition-metal-catalyzed allylic substitution of al-
lylic compounds represents a very useful procedure for
the construction of allylic substituted compounds, and
several different nucleophiles have been employed in this
type of reaction.1 On the other hand, compounds contain-
ing a cyano group are synthetically useful because the cy-
ano substituent can easily be converted into other
functionalities; metal cyanides, such as potassium cyanide
(KCN) and sodium cyanide (NaCN) were mainly used as
the source of the cyano group. As an alternative cyanating
reagent, trimethylsilyl cyanide (TMSCN), which is easy
to handle and even reacts with several secondary or cyclic
compounds, including allylic substrates, in common or-
ganic solvents, is also widely used.2,3 To the best of our
knowledge, however, there is only a single example of the
metal-catalyzed allylic substitution of allylic compounds
with trimethylsilyl cyanide as the cyanating reagent.3 In
1993, Tsuji described the palladium-catalyzed allylic cy-
anation of allylic esters with trimethylsilyl cyanide.3
Based on this background, we initiated a study to realize
the allylic cyanation of allylic compounds with trimethyl-
silyl cyanide using alternative transition metal catalysts,
and we report herein the copper-catalyzed allylic cyana-
tion of allyl chlorides and allyl esters with trimethylsilyl
cyanide.
Ph
2b X = OAc
5
Entry
Substrate [Cu]
(mol%)
Solvent
Yield
(%)a
Ratio
of 4:5b
1
2
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1c
1c
1d
2a
2b
–
MeCN
MeCN
MeCN
MeCN
MeCN
DMF
0
9
–
CuCl (5)
CuBr (5)
CuI (5)
>98:2
>98:2
>98:2
–
3
67
87
0
4
5
CuOTf (5)
CuI (5)
6
53
32
0
>98:2
>98:2
>98:2
>98:2
–
7
CuI (5)
DMSO
DME
8
CuI (5)
9
CuI (5)
THF
<5
0
10
11
12
13
14c
15c
16c
17
CuI (5)
toluene
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
CuI (5)
29
50
<5
77
23
76
80
>98:2
>98:2
>98:2
>98:2
>98:2
>98:2
>98:2
CuI (25)
CuI (25)
CuI (25)
CuI (25)
CuI (5)
We initially examined the reaction of cinnamyl chloride
(1a) with trimethylsilyl cyanide (3) in acetonitrile without
a catalyst, but did not obtain any products (Table 1, entry
1). Subsequent screening with the aim of finding an effec-
CuI (25)
a Yield of isolated product 4.
SYNTHESIS 2014, 46, 2747–2750
Advanced online publication: 09.07.2014
DOI: 10.1055/s-0034-1378322; Art ID: ss-2014-f0264-op
© Georg Thieme Verlag Stuttgart · New York
b Ratio was determined by 1H NMR spectroscopy of the crude prod-
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
ucts.
c Reaction was conducted at 80 °C.

2748
D. Munemori et al.
PAPER
reaction to give cyanide 4 (Table 1, entries 2–5). Cop- (35%), the regioselectivity was the same as that obtained
per(I) iodide (CuI) exhibited the highest catalyst activity in the reaction of 10b (Table 2, entry 8).
providing an 87% yield of isolated product 4 (Table 1, en-
Table 2 Cyanation of Disubstituted Allylic Substrates
try 4). We also confirmed that the reaction proceeded with
high regioselectivity and linear allylic cyanide 4 was ob-
CN
X
tained as a single regioisomer. Next, we examined the in-
fluence of the solvent on the cyanation reaction; solvents
Ph
Ph
12
10a X = Cl
10b X = OAc
including N,N-dimethylformamide, dimethyl sulfoxide,
1,2-dimethoxyethane (DME), tetrahydrofuran and tolu-
ene all proved inferior in comparison with acetonitrile
(Table 1, entries 6–10). We next investigated the reaction
of other cinnamyl-based compounds 1b–d using the cop-
per(I) iodide catalyst. The reaction of cinnamyl bromide
(1b) gave a low yield (29%), and the yield could only be
increased to 50% when using 25 mol% of copper(I) iodide
(Table 1, entries 11 and 12). Decreased reactivity was also
observed for the allylic carbonate 1c, but we succeeded in
obtaining an improved 77% yield of product 4 by increas-
ing the reaction temperature from 60 °C to 80 °C (Table
1, entries 13 and 14). Unfortunately, the reaction of cin-
namyl acetate (1d) resulted in only a 23% yield of cyanide
4 (Table 1, entry 15). Furthermore, we examined the reac-
tion of branched allylic esters 2a and 2b and obtained the
desired product 4 in yields of 76% (5 mol% of CuI) and
80% (25 mol% of CuI, at 60 °C), respectively (Table 1,
entries 16 and 17). These results indicate that the reactiv-
ity of branched allylic esters 2 is higher than that of cin-
namyl allylic esters 1 in the copper(I) iodide catalyzed
allylic cyanation with trimethylsilyl cyanide. We also
found that the allyl chlorides 6 and 8 possessing an alkyl
group provided allylic cyanides 7 and 9 in good yields un-
der our optimized conditions (Scheme 1).
cat. [Cu]
+
Me3SiCN
and/or
MeCN
80 °C, 12 h
OAc
3
CN
Ph
Ph
11
13
Entry
Substrate
[Cu] (mol%)
Yield (%)a
Ratio of
12:13b
1c
2
10a
10b
10b
10b
10b
10b
10b
11
CuI (25)
67
<5
33
26
0
>98:2
>98:2
>98:2
>98:2
–
CuI (25)
3
CuBr (25)
CuCl (25)
CuOTf (25)
CuCN (25)
CuCN (25)
CuCN (25)
4
5
6
38
68
35
>98:2
>98:2
>98:2
7d
8
a Yield of isolated product 12.
b Ratio was determined by 1H NMR spectroscopy of the crude prod-
ucts.
c Reaction was conducted at 60 °C.
d The reaction time was 36 h.
CuI (5 mol%)
Me3SiCN
Despite succeeding in realizing the allylic cyanation of
1,3-disubstituted allylic compounds 10a and 10b, we
found that copper(I) cyanide did not catalyze the cyana-
tion reaction of 1,3-diphenylallyl acetate (14) (Table 3,
entry 1). Once again, we screened several copper catalysts
and found that copper(I) iodide and copper(I) bromide
(CuBr) provided the desired cyanated product 15 (Table
3, entries 2 and 3). Although copper(I) cyanide and cop-
per(I) bromide exhibited similar catalytic activity with
10b (Table 2, entries 3 and 6), these catalysts showed dif-
ferent activity in the cyanation of allylic acetate 14 (Table
3, entries 1 and 3). The reason for such a difference is not
clear, but the steric interaction between the methyl or phe-
nyl group of the allylic substrate and the cyanide or bro-
mine ligand on the copper salt might be responsible for the
observed results. Furthermore, we found that some cop-
per(II) salts also catalyzed the desired cyanation reaction
(Table 3, entries 4–6). In particular, copper(II) chloride
(CuCl2) demonstrated acceptable catalytic activity for the
cyanation of 14, and provided allylic cyanide 15 in 79%
yield (Table 3, entry 6).
Cl
CN
MeCN, 60 °C
12 h
6
7 (74%)
CuI (5 mol%)
Me3SiCN
Ph
Cl
Ph
CN
MeCN, 60 °C
12 h
8
9 (86%)
Scheme 1 Allylic cyanation of allylic chlorides 6 and 8 possessing
an alkyl group
We next examined the copper-catalyzed allylic cyanation
of 1,3-disubstituted allylic substrates. As shown in Table
2, the reaction of allylic chloride 10a proceeded smoothly
to give the allylic cyanide 12 as a single regioisomer (Ta-
ble 2, entry 1); in contrast, allyl acetate 10b exhibited low-
er reactivity and gave the desired product in a very low
yield (Table 2, entry 2).6 Therefore, we reinvestigated the
effect of different copper catalysts for the cyanation of
10b and found that copper(I) cyanide (CuCN) catalyzed
the formation of product 12 in an acceptable 68% yield,
albeit a longer reaction time (36 h) was required (Table 2,
entries 6 and 7). Although the reaction of allylic acetate
11, which is a regioisomer of 10b, resulted in a low yield
We further conducted two reactions to gain an insight into
the reaction mechanism. The reaction of enantiomerically
enriched allyl acetate (S)-10b (99% ee) gave racemic
Synthesis 2014, 46, 2747–2750
© Georg Thieme Verlag Stuttgart · New York

PAPER
Copper-Catalyzed Regioselective Allylic Cyanations
2749
60N (spherical, neutral, 63–210 μm). Melting points were recorded
using a Yanaco MP-500P apparatus. IR spectra were measured on a
Jasco FT/IR-4100 spectrophotometer. NMR spectra were recorded
in CDCl3 at 25 °C on a JEOL EX-250 spectrometer (270 MHz for
1H, 67 MHz for 13C), a JEOL JNM ECP-500 spectrometer (500
MHz for 1H and 125 MHz for 13C) or a Bruker Biospin AVANCE
II 600 (600 MHz for 1H and 150 MHz for 13C). Chemical shifts (δ)
are reported in ppm and are referenced to an internal standard
(SiMe4) for 1H NMR, and residual chloroform (δ 77.0) as an internal
reference for 13C NMR. High-resolution mass spectra (HRMS)
were obtained using a JEOL JMS-T100LP instrument.
Table 3 Cyanation of 1,3-Diphenylallyl Acetate
OAc
CN
cat. [Cu]
+
3
MeCN
80 °C, 12 h
Ph
Ph
Ph
Ph
14
15
Entry
[Cu] (mol%)
Yield (%)a
1
2
3
4
5
6
CuCN (25)
CuI (25)
0
59
70
50
63
79
(E)-4-Phenylbut-3-enenitrile (4);8b Typical Procedure
A solution of CuI (2.7 mg, 0.014 mmol), cinnamyl chloride (1a) (43
mg, 0.28 mmol) and TMSCN (3) (56 mg, 0.56 mmol) in anhydrous
MeCN (1.0 mL) was stirred at 60 °C for 12 h. The mixture was
quenched with H2O and extracted with EtOAc (3 × 2 mL). The
combined organic layer was dried over MgSO4 and concentrated in
vacuo. The residue was chromatographed on silica gel (hexane–
EtOAc, 4:1) to give allylic cyanide 4.
CuBr (25)
Cu(OAc)2 (25)
CuBr2 (25)
CuCl2 (25)
a Yield of isolated product.
Yield: 35 mg (87%); brownish solid; mp 54–55 °C.
IR (neat): 3025, 2923, 2254, 1412, 968, 737, 692 cm–1.
1H NMR (600 MHz, CDCl3): δ = 7.38–7.27 (m, 5 H), 6.74 (dt, J =
15.8, 1.8 Hz, 1 H), 6.06 (dt, J = 15.8, 5.6 Hz, 1 H), 3.30 (dd, J = 5.6,
1.8 Hz, 2 H).
13C NMR (150 MHz, CDCl3): δ = 135.7, 134.6, 128.8, 128.3, 126.5,
117.4, 116.8, 20.8.
HRMS (ESI): m/z [M + H]+ calcd for C10H10N: 144.0813; found:
product 12 in 61% yield under the optimized conditions
(Scheme 2, eq 1). The formation of racemic product 12
suggests that the reaction proceeded through a radical
pathway. To clarify this hypothesis, we ran the copper(I)
cyanide catalyzed reaction of 10b with trimethylsilyl cya-
nide (3) in the presence of 2,2,6,6-tetramethyl-1-piperidi-
nyloxy free radical (TEMPO) (1 equiv with respect to
10b), and found that the allylic cyanation did not occur
(Scheme 2, eq 2). From these results, we concluded that
the copper-catalyzed allylic cyanation of allylic com-
pounds with trimethylsilyl cyanide proceeds through a
radical pathway.7
144.0820.
(E)-4-Cyclohexylbut-3-enenitrile (7)
Yield: 31 mg (74%); pale yellow oil.
IR (KBr): 2925, 2249, 1449, 970 cm–1.
1H NMR (500 MHz, CDCl3): δ = 5.76 (dd, J = 15.8, 6.9 Hz, 1 H),
5.32–5.27 (m, 1 H), 3.05 (d, J = 5.5 Hz, 2 H), 2.03–1.98 (m, 1 H),
1.74–1.64 (m, 4 H), 1.31–1.22 (m, 3 H), 1.19–1.06 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 141.8, 117.8, 114.7, 40.3, 32.4,
25.9, 25.7, 20.4.
HRMS (ESI): m/z [M + H]+ calcd for C10H16N: 150.1283; found:
150.1277.
OAc
CN
CuCN (25 mol%)
+
3
3
(1)
(2)
Ph
Ph
Ph
MeCN
80 °C, 36 h
(S)-10b
(99% ee)
12
(61% yield, 0% ee)
OAc
CuCN (25 mol%)
+
no reaction
(E)-6-Phenylhex-3-enenitrile (9)
Yield: 42 mg (86%); pale yellow oil.
IR (KBr): 3026, 2927, 2249, 1496, 1454, 969, 748 cm–1.
TEMPO
MeCN
80 °C, 96 h
10b
1H NMR (500 MHz, CDCl3): δ = 7.26 (t, J = 7.4 Hz, 2 H), 7.16 (dd,
J = 16.6, 7.4 Hz, 3 H), 5.85–5.79 (m, 1 H), 5.34–5.28 (m, 1 H), 2.96
(d, J = 5.7 Hz, 2 H), 2.67 (t, J = 7.6 Hz, 2 H), 2.35 (q, J = 7.6 Hz, 2
H).
13C NMR (125 MHz, CDCl3): δ = 141.0, 134.9, 128.24, 128.18,
125.8, 117.8, 117.5, 35.0, 33.7, 20.1.
Scheme 2 Mechanistic investigations
In summary, we have demonstrated the copper-catalyzed
allylic cyanation of allylic compounds with trimethylsilyl
cyanide and found that the reactions provide allylic cya-
nides with high regioselectivity. Although the selection of
appropriate copper catalyst depends on the type of allylic
substrate employed, we succeeded in realizing the cyana-
tion of mono- and 1,3-disubstituted allylic compounds
with trimethylsilyl cyanide. We further discovered that
the reaction proceeds via a radical pathway.
HRMS (ESI): m/z [M + H]+ calcd for C12H14N: 172.1126; found:
172.1106.
(E)-2-Methyl-4-phenylbut-3-enenitrile (12)2g
A solution of CuCN (5.9 mg, 0.066 mmol), (E)-4-phenylbut-3-en-
2-yl acetate (10b) (50 mg, 0.26 mmol) and TMSCN (3) (52 mg, 0.52
mmol) in anhydrous MeCN (1.0 mL) was stirred at 80 °C for 36 h.
The mixture was quenched with H2O and extracted with EtOAc
(3 × 2 mL). The combined organic layer was dried over MgSO4 and
concentrated in vacuo. The residue was chromatographed on silica
gel (hexane–EtOAc, 4:1) to give allylic cyanide 12.
All reactions were carried out under a nitrogen atmosphere. Allylic
compounds 1c,8 2,9 6,10 8,10 1010 and 1110 were prepared according
to the literature. All other allylic compounds (1a, 1b, 1d and 14) and
other chemicals/reagents, including the copper salts, were pur-
chased from commercial sources and used without further purifica-
tion. Column chromatography was performed on Kanto silica gel
Yield: 28 mg (68%); colorless oil.
IR (neat): 3029, 2986, 2242, 1450, 966, 748, 694, 505 cm–1.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 2747–2750

2750
D. Munemori et al.
PAPER
Yamada, N.; Tanaka, S.; Ebihara, M.; Kawamura, T.
1H NMR (600 MHz, CDCl3): δ = 7.38–7.26 (m, 5 H), 6.71 (dd, J =
15.8, 6.1 Hz, 1 H), 6.06 (dd, J = 15.8, 6.1 Hz, 1 H), 3.50 (m, 1 H),
1.50 (d, J = 7.3 Hz, 3 H).
13C NMR (150 MHz, CDCl3): δ = 135.7, 132.5, 128.8, 128.3, 126.6,
124.3, 120.9, 28.4, 19.1.
HRMS (ESI): m/z [M + H]+ calcd for C11H12N: 158.0970; found:
158.0959.
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(E)-2,4-Diphenylbut-3-enenitrile (15)2g
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(6) We also found that the reactions of substrates 10a and 10b
with NaCN resulted in no reaction at 80 °C in MeCN.
(7) (a) Nishikata, T.; Noda, Y.; Fujimoto, R.; Sakashita, T.
J. Am. Chem. Soc. 2013, 135, 16372. (b) Presset, M.;
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2011, 50, 9120. (f) Jakubowski, W.; Tsarevsky, N. V.;
Higashihara, T.; Faust, R.; Matyjaszewski, K.
A solution of CuCl2 (6.7 mg, 0.050 mmol), (E)-1,3-diphenylallyl
acetate (14) (50 mg, 0.20 mmol) and TMSCN (3) (39 mg, 0.40
mmol) in anhydrous MeCN (1.0 mL) was stirred at 80 °C for 12 h.
The mixture was quenched with H2O and extracted with EtOAc
(3 × 2 mL). The combined organic layer was dried over MgSO4 and
concentrated in vacuo. The residue was chromatographed on silica
gel (hexane–EtOAc, 4:1) to give allylic cyanide 15.
Yield: 34 mg (79%); white solid; mp 70–71 °C.
IR (KBr): 3061, 3027, 2907, 2240, 1494, 1449, 972, 747, 691 cm–1.
1H NMR (270 MHz, CDCl3): δ = 7.39–7.22 (m, 10 H), 6.80 (d, J =
15.8 Hz, 1 H), 6.18 (dd, J = 15.8, 6.3 Hz, 1 H), 4.67 (dd, J = 6.3, 1.0
Hz, 1 H).
13C NMR (67 MHz, CDCl3): δ = 135.4, 134.5, 133.3, 129.2, 128.7,
128.4, 127.5, 126.7, 123.3, 118.7, 40.0.
HRMS (ESI): m/z [M + H]+ calcd for C16H14N: 220.1126; found:
220.1133.
Acknowledgment
This work was partially supported by Individual Research Expense
of the College of Humanities and Sciences at Nihon University for
2014.
Supporting Information for this article is available online
at
http://www.thieme-connect.com/products/ejournals/journal/
10.1055/s-00000084.SunpfgIpi
m
o
nr
i
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