Nickel-catalyzed dimerization coupling reactions of vinyl Grignard reagents with 3, 4-membered cyclic ethers and chlorosilanes

Article abstract of DOI:10.1016/j.tet.2007.04.013

Vinyl Grignard reagents reacted with cyclic ethers in the presence of a nickel catalyst giving rise to 2:1 coupling products 1 regioselectively. When chlorosilanes were used instead of cyclic ethers, 2:2 component coupling products 6 were obtained. A plau

Full text of DOI:10.1016/j.tet.2007.04.013

Tetrahedron 63 (2007) 6635–6641
Nickel-catalyzed dimerization coupling reactions of vinyl
Grignard reagents with 3, 4-membered cyclic
ethers and chlorosilanes
*
Yuuki Fujii, Jun Terao, Hiroyasu Watabe, Hiroyuki Watanabe and Nobuaki Kambe
*
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Received 15 February 2007; revised 29 March 2007; accepted 9 April 2007
Available online 13 April 2007
Dedicated to the late Emeritus Professor Yoshihiko Ito of Kyoto University
Abstract—Vinyl Grignard reagents reacted with cyclic ethers in the presence of a nickel catalyst giving rise to 2:1 coupling products 1
regioselectively. When chlorosilanes were used instead of cyclic ethers, 2:2 component coupling products 6 were obtained. A plausible
reaction pathway via 1,3-butadiene–nickel complex and (2-butene-1,4-diyl)magnesium was proposed.
Ó 2007 Published by Elsevier Ltd.
1
. Introduction
was stirred for 3 h at the same temperature. The NMR anal-
ysis of the crude mixture indicated the formation of trans-
2-(1-methyl-2-propenyl)cyclopentanol 1a in 79% yield. The
product was obtained as 1:1.3 mixture of diastereomers in
66% yield by column chromatography with pentane/
ether¼6:4 as the eluent (Table 1, entry 1). Entry 2 shows
a successful example of large scale preparation (50 mmol
of cyclopentene oxide) under the identical conditions, where
5.07 g (72%) of 1a was obtained in pure form by distillation.
When NiCl was used instead of NiCl (PPh ) , 1a was
Since the discovery of the formation of Grignard reagents by
the reaction of organic halides with magnesium metal in
1901, numerous efforts have been devoted to developing
their synthetic applications especially to carbon–carbon
bond forming reactions. Epoch-making in this field was
the introduction of transition metal catalysts in Grignard
chemistry that provided novel synthetic methodologies by
1
a
1
1
e–h
cross-coupling reactions.
We have been working on
2
2
3 2
C–C and C–Si bond forming reactions using Grignard re-
agents catalyzed by Zr, Ti, Ni, or Pd involving ate-complex
intermediates. During the course of these studies, we have
formed in 62% NMR yield (entry 3). Under the same condi-
tions, PdCl (PPh ) and Cp TiCl were ineffective (entries 4
2
3 2
2
2
2
and 5). When cyclododecene oxide (trans/cis¼33:67) was
used, only cis-cyclododecene oxide reacted with vinyl
Grignard reagent to afford coupling product 1b as 1:1 mix-
recently found that Ni catalyzes the alkylative dimerization
of vinyl Grignard reagents with alkyl fluorides giving rise to
3
4
2
-alkyl-3-butenyl Grignard reagents. As an extension of this
ture of diastereomers (entry 6). Isobutylene oxide gave cou-
work, we report herein Ni-catalyzed regioselective coupling
of vinyl Grignard reagents with cyclic ethers and chlorosi-
lanes to give 2:1 or 2:2 coupling products, respectively.
pling product 1c in poor yield (20%) (entry 7). The use of
oxetanes also afforded the corresponding 2:1 coupling prod-
ucts 1d and 1e in 62% and 50% yields, respectively (entries 8
and 9). However, no reaction took place with substituted
vinyl Grignard reagents such as MeCH]CHMgBr, CH ]
2
2
. Results and discussion
CMeMgBr and PhCH]CHMgBr.
2.1. Nickel-catalyzed 2:1 coupling reaction of vinyl
Grignard reagents with cyclic ethers
When a reaction of cyclopentene oxide with vinyl
Grignard reagent was quenched with D O, 79% yield of
2
monodeuterated compound 3 (d-content 94%) as 1:1.3
mixture of diastereomers was formed. This result implies
that the butenyl Grignard reagent 2 is formed in the pres-
ent reaction. As a synthetic application of thus-formed 2,
we attempted to synthesize bicyclic ester 5 via intramole-
cular esterification of 4 formed by the reaction of 2 with
A typical example is as follows. To a mixture of cyclopen-
tene oxide (1.0 mmol) and NiCl (PPh ) (0.03 mmol) was
added vinyl magnesium chloride (2.2 mmol) in THF
2
3 2
ꢀ
(
1.7 mL) at 25 C under nitrogen, and the resulting mixture
CO . Into a solution of 2 prepared in situ under similar
2
conditions of entry 1 in Table 1, dry ice was added at
*
Corresponding authors. Tel.: +81 6 6879 7388; fax: +81 6 879 7390;
e-mail: kambe@chem.eng.osaka-u.ac.jp
0
040–4020/$ - see front matter Ó 2007 Published by Elsevier Ltd.
doi:10.1016/j.tet.2007.04.013

6636
Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
Table 1. Ni-catalyzed 2:1 coupling reaction of vinyl Grignard reagent with
cyclic ethers
of 77:23. No evidence for the formation of regioisomers of
a was detected. The product was obtained in pure form in
a
6
NiCl2(PPh3)2 (3 mol%) H+
THF, 25 °C, 3 h
H
O
66% yield by a recycling preparative HPLC using CHCl3
as an eluent (Table 2, entry 1). In this reaction, tributylvinyl-
silane was formed in 3% yield as a byproduct probably via
MgCl
+
OH
n
n
(
n = 1,2)
the direct reaction of vinyl magnesium chloride with
Bu SiCl. Other trialkyl and phenyl substituted chlorosi-
b
Yield (%)
n
Entry
Epoxide (oxetane)
Product
3
lanes afforded the corresponding 2:2 coupling products in
good yield (entries 3–6). When Cp TiCl was used instead
of NiCl (PPh ) , 6a was obtained in 37% NMR yield (entry
1
2
3
4
5
79 (66)
c
O
H
d(72)
2
2
1a
1b
1c
62
OH
2
3 2
e
0
5
2
), whereas no reaction took place with PdCl (PPh ) .
2 3 2
f
0
O
H
Table 2. Ni-catalyzed 2:2 coupling reaction of vinyl Grignard reagent with
chlorosilanes
a
OH
6
66 (61)
NiCl2(PPh3)2 (3 mol%)
THF, 25 °C, 3 h
R3Si
MgCl
+
R3Si-Cl
SiR3
(
trans/cis = 33/67)
b
Yield (%) E/Z
c
Entry Chlorosilane
Product
H
OH
O
g
7
8
25 (20)
1
2
n
n
nBu3Si
86 (66)
37
77/23
79/21
d
Bu
3
Si–Cl
n
6a
Si Bu3
nPr Si
3
3
4
5
6
a
Pr
3
Si–Cl
Si–Cl
MeSi–Cl
n
6b 84 (69)
6c 79 (58)
79/21
77/23
60/40
71/29
Si Pr3
H
O
O
1d
1e
73 (62)
64 (50)
Et3Si
Et
3
SiEt3
OH
Ph2MeSi
Ph
2
6d
(48)
SiPh2Me
H
e
3
Ph Si
9
3
Ph Si–Cl
6e 82 (79)
SiPh3
OH
ꢀ
The reaction was carried out in THF at 25 C for 3 h using chlorosilane
a
ꢀ
The reaction was carried out in THF at 25 C for 3 h using epoxide/oxe-
(1.0 mmol), vinyl Grignard reagent (1.5 mmol) and NiCl
(0.03 mmol).
2 3 2
(PPh )
tane (1.0 mmol), vinyl Grignard reagent (2.2 mmol) and NiCl
(0.03 mmol).
2 3 2
(PPh )
b
c
d
e
NMR yield. Isolated yield is in parentheses.
Determined by GC or NMR.
Cp TiCl was used as a catalyst.
b
c
d
e
f
NMR yield. Isolated yield is in parentheses.
Reaction was carried out on a 50 mmol scale.
2
2
ꢀ
NiCl
Cp TiCl
PdCl (PPh
2
was used.
was used.
was used.
At 0 C, 5 h.
2
2
2
3
)
2
No reaction took place when MeCH]CHMgBr and
CH ]CMeMgBr were used, although coupling product 7
g
Reaction was carried out on a 3.0 mmol scale.
2
was obtained in 71% yield from PhCH]CHMgBr (Eq. 2).
We have already reported that Cp TiCl catalyzes similar di-
ꢀ
for 2 h, the desired bicyclic ester 5 was obtained in 37%
yield (Eq. 1).
ꢀ
2
5 C. After treating with 3 N HCl and stirring at 40 C
2
2
merization silylation of vinyl Grignard reagent with chloro-
silanes. However, in this Ti-catalyzed reaction system,
5
O
MgCl
D
D+ / H+
NiCl2(PPh3)2 (3 mol%)
+
MgCl
OMgCl
OH
THF, 25 °C, 3 h
2
3; 79% (94% d)
CO2 then H+
ð1Þ
O
O
COOH
OH
4
0 °C, 2 h
4
5; 37%
2.2. Nickel-catalyzed 2:2 coupling reaction of vinyl
Grignard reagents with chlorosilanes
substituted Grignard reagents including PhCH]CHMgBr
did not afford the corresponding products 7 at all.
When chlorosilanes were employed instead of cyclic ethers,
dimerization disilylation proceeded regioselectively under
identical conditions to afford 1,4-disilyl-2-butenes (6). For
NiCl (PPh )
2
3 2
Ph
(
3 mol%)
Ph
nBu3Si-Cl
3
Bu Si
+
MgBr
SiBu3
n
THF, 25 °C, 3 h
example, Bu SiCl (1.0 mmol) reacted with vinyl magne-
3
Ph
; 71% (E/Z = 81/19)
sium chloride (1.5 mmol) in THF (1.2 mL) in the presence
of NiCl (PPh ) (0.03 mmol) at 25 C for 3 h to give 1,4-
7
ꢀ
bis(tributylsilyl)-2-butene 6a in 86% yield with an E/Z ratio
2
3 2
ð2Þ

Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
6637
2
.3. Reaction mechanisms
order to confirm the intermediary of 13 in the present reac-
tion system, we conducted the reaction of NiCl (PPh )
2
3 2
Plausible reaction pathways for the present reaction are out-
lined in Scheme 1. Nickel(II) is reduced by vinyl Grignard
reagent to afford Ni(0) via the divinylnickel complex
(0.03 mmol) with vinyl magnesium chloride (1.5 mmol) at
25 C in the absence of cyclic ethers and chlorosilanes. After
ꢀ
stirring for 3 h, the reaction mixture was treated at 25 C for
ꢀ
6
8
another vinyl Grignard reagent to afford the p-allylnickel
. Thus-formed butadiene–nickel complex 9 reacts with
15 min with cyclopentene oxide and tributylchlorosilane
separately. GC analysis of the resulting reaction mixture
showed the formation of 1d and 6a in 70% yield (Eqs. 3
and 4). The elongation of reaction time to 3 h did not
improve the products’ yields at all. These results suggest
that 13 is formed from vinyl Grignard reagents in the
presence of Ni. When the reaction was conducted using
Cp TiCl instead of NiCl (PPh ) under the identical condi-
7
complex 11 via nickelate complex 10. Transmetallation of
1
1 with vinyl Grignard reagent affords 8 and (2-butene-1,4-
diyl)magnesium 13 via diallyl Grignard reagent 12. Com-
pound 13 (and/or 12) reacts with cyclic ethers at an internal
carbon to give 1 and with chlorosilanes at a terminal carbon
to give 6. Alternatively, direct reaction of 10 with cyclic
ethers and chlorosilanes may form the corresponding cou-
pling products 1 or 6 along with regeneration of 8 via vinyl
nickel intermediates 14 or 16, respectively. Although a possi-
bility of these alternative pathways cannot be ruled out, the
following evidence supports the formation of 13 in this reac-
tion system.
2
2
2
3 2
tions and by the same procedure as Eq. 3, 1d was not
formed. Although these yields were slightly lower than
the results of one pot reaction system as shown in entry 1
of Tables 1 and 2, this method can be applied to more
reactive electrophiles that are not tolerant to vinyl Grignard
reagent. For example, homoallylic amine 18 was obtained
as a mixture of diastereomers (erythro/threo¼94:6) by the
1
0
It is known that (2-butene-1,4-diyl)magnesiums react with
epoxides at the b-carbon to give the corresponding
reaction of thus-formed 13 with imine 17, which cannot
be used in one pot reaction system since the direct reaction
of vinyl Grignard reagent with imine predominates (Eqs. 5
and 6).
8
2
-alkyl-3-butenyl Grignard reagents and react with chloro-
silanes at a-carbon giving rise to 1,4-disilyl-2-butenes. In
9
NiCl2Ln
MgCl
MgCl
R3Si
SiR3
nOMgCl
6
Ni
8
1
R3Si-Cl
_
MgCl
SiR3
Ni
+
MgCl
16
Ni
OMgCl
Ni
9
n
MgCl
14
SiR3
MgCl
Ni
15
_
+
O
n
Ni
R3Si-Cl
MgCl
10
MgCl
Ni
11
O
n
MgCl
1
_
MgCl2
MgCl2
ClMg
+
Ni
MgCl
Mg
8
12
13
R3Si-Cl
6
Scheme 1. A plausible reaction pathway.

6638
Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
O
H+
(
1.0 mmol)
H
(3)
2
5 °C, 15 min
OH
1d; 70%
nBu3Si-Cl
NiCl2(PPh3)2 (0.03 mmol)
THF, 25 °C, 3 h
(1.0 mmol)
5 °C, 15 min
nBu3Si
n
MgCl
Si Bu
(4)
2
3
Mg
2
.0 mmol
6a; 70%
13
Ph
N
17
Ph
H
H+
(
1.0 mmol)
Ph
(5)
(6)
-
78 °C, 30 min
Ph
N
H
then 0 °C, 30 min
1
8; 58%
Ph
N
H+
NiCl2(PPh3)2 (0.03 mmol)
THF, 25 °C, 3 h
MgCl
+
1
8; 0%
Ph
H
2.0 mmol
1.0 mmol
3
. Conclusion
chlorotriethylsilane (Shin-Etsu Chemical Company), chloro-
triphenylsilane, chlorotributylsilane, chlorotripropylsilane
(Aldrich Chemical Company), cyclopentene oxide, isobutyl-
ene oxide, oxetane, 3,3-dimethyl oxetane, diphenylmethyl-
chlorosilane, benzylideneaniline, NiCl (PPh ) (Tokyo
In conclusion, we have developed Ni-catalyzed regioselec-
tive coupling of vinyl Grignard reagents with cyclic ethers
or chlorosilanes to give 2:1 and 2:2 coupling products, re-
spectively. The present reaction may involve the formation
of (2-butene-1,4-diyl)magnesium (13) from vinyl Grignard
reagents by the aid of Ni catalysts and its electrophilic trap-
ping with cyclic ethers or chlorosilanes. This reaction would
provide a new method for generation of (2-butene-1,4-diyl)-
magnesium species (13) from vinyl Grignard reagents by Ni
catalyst as an addition to known methods using 1,3-butadi-
ene and activated Mg. Mechanistic details are currently
under investigation.
2
3 2
Chemical Industry Company) were purchased and used as
received.
4.2. General procedure for nickel-catalyzed 2:1 coupling
reaction of vinyl Grignard reagents with cyclic ethers
(Table 1)
To a mixture of cyclic ethers (1.0 mmol) and NiCl (PPh )
2
3 2
(19.6 mg, 0.03 mmol) was added vinyl magnesium chloride
ꢀ
(1.30 M in THF, 1.7 mL, 2.2 mmol) at 25 C. After stirring
for 3 h, aqueous 1 N HCl was added and the products were
extracted with ether. The organic layer was dried over
MgSO and evaporated to give crude products. Purification
4. Experimental
4
4
.1. General experimental method
by column chromatography on silica gel gave the corre-
sponding products (1a–1e).
1
13
H NMR and C NMR spectra were recorded with a JEOL
JNM-Alice 400 (400 MHz and 100 MHz, respectively)
spectrometer. Chemical shifts are reported in parts per mil-
lion (d) downfield from internal tetramethylsilane. Infrared
spectra were recorded with a Perkin–Elmer FT-IR (Model
4.2.1. trans-2-(1-Methyl-2-propenyl)cyclopentanol (1a).
Purification by column chromatography on silica gel (pen-
tane/ether¼6:4) gave 90 mg (66%) of 1a (96% purity deter-
mined by GC). The following spectral and analytical data
were obtained from 1:1.3 mixture of diastereomers. IR
(NaCl): 3344, 2957, 2876, 1639, 1452, 1343, 1027, 996,
1
600). Both conventional and high resolution mass spectra
were recorded with a JEOL JMS-DX303HF spectrometer.
GC mass spectra (EI) were obtained using a JMS-mate oper-
ating in the electron impact mode (70 eV) equipped with an
RTX-5 30MX.25MMX.25U column. HPLC separations
were performed on a recycling preparative HPLC (Japan An-
alytical Industry Co. Ltd., Model LC-908) equipped with
ꢁ
1 1
911 cm ; H NMR (400 MHz, CDCl ): d 5.87–5.69 (m,
3
1H), 5.10–4.95 (m, 2H), 3.99–3.90 (m, 1H), 2.25–2.16
(m, 0.6H), 2.08–1.99 (m, 0.4H), 1.93–1.53 (m, 6H), 1.31–
1.20 (m, 2H), 1.08 (d, J¼6.8 Hz, 1.7H), 1.01 (d,
1
3
J¼6.6 Hz, 1.3H); C NMR (100 MHz, CDCl ) (major
3
JAIGEL-1H and -2H columns (GPC) using CHCl as an
3
and minor): d (142.2, 144.2), (113.64, 113.62), (76.5,
77.3), (53.5, 53.4), (40.1, 42.8), (35.4, 34.4), (27.6, 28.9),
(22.4, 21.7), (18.6, 18.9); MS (CI) m/z (relative intensity,
%): 141 (M+1, 14), 124 (9), 123 (100), 84 (3), 81 (9), 67
(3); HRMS (CI) calcd for C H O (M+1): 141.1201, found:
eluent. Column chromatography was conducted using Kanto
Chemical Co., Inc. silica gel 60 (63–210 mm). Elemental
analyses were performed on a Perkin Elmer 240C apparatus.
GC yields were determined using octane as an internal stan-
dard. Vinyl Grignard reagent (Kanto Chemical Company),
9
17
141.1264.

Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
6639
4
.2.2. trans-2-(1-Methyl-2-propenyl)cyclododecanol (1b).
(m, 1H), 1.42–1.36 (m, 2H), 1.22 (dd, J¼14.0 Hz, 3.6 Hz,
1H), 1.01 (d, J¼6.8 Hz, 3H), 0.90 (s, 3H), 0.89 (s, 3H);
Purification by column chromatography on silica gel (hex-
ane/ether¼9:1) gave 145 mg (61%) of 1b (97% purity deter-
mined by GC) as a mixture of diastereomers derived from
cis-1,2-epoxycyclododecane with ca. 1:1 ratio indicated by
1
3
C NMR (100 MHz, CDCl ): d 146.5, 112.0, 71.7, 45.4,
3
35.9, 34.6, 25.2, 24.4, 23.9; MS (CI) m/z (relative intensity,
%): 143 (M+1, 100), 126 (3), 125 (32), 83 (7), 69 (19);
HRMS (CI) calcd for C H O (M+1): 143.1358, found:
1
13
H and C NMR. A 1:1 mixture of diastereomers. IR
NaCl): 3382, 2932, 2863, 1636, 1469, 1445, 1001,
9
19
(
143.1437.
ꢁ
1 1
9
1
0
07 cm ; H NMR (400 MHz, CDCl ): d 6.05–5.92 (m,
3
H), 5.10–4.98 (m, 2H), 3.79–3.72 (m, 1H), 2.68–2.58 (m,
.5H), 2.58–2.50 (m, 0.5H), 1.74–1.25 (m, 22H), 1.08 (d,
4.3. trans-2-(1-Deuteriomethyl-2-propenyl)cyclo-
pentanol (3)
1
3
J¼7.1 Hz, 1.5H), 1.05 (d, J¼7.1 Hz, 1.5H); C NMR
(
100 MHz, CDCl ): d 144.7, 143.9, 113.8, 112.6, 72.0,
3
To a mixture of cyclopentene oxide (84.0 mg, 1.00 mmol)
and NiCl (PPh ) (19.6 mg, 0.03 mmol) was added vinyl
magnesium chloride (1.35 M in THF, 1.6 mL, 2.2 mmol) at
7
2
2
1.7, 43.6, 43.5, 37.6, 37.0, 32.9, 32.6, 25.2, 24.8, 24.6,
4.53, 24.50, 24.33, 24.27, 24.13, 24.11, 24.06, 23.99 (2C),
3.92, 23.7, 23.6, 23.4, 21.2, 21.1, 18.0, 16.5; MS (EI) m/z
2
3 2
ꢀ
25 C. After stirring for 3 h, D O was added and the products
2
+
(
relative intensity, %): 238 (M , 12), 123 (10), 121 (12),
were extracted with ether. The organic layer was dried over
MgSO and evaporated to give yellow crude products (79%
1
9
8
6
11 (16), 110 (10), 109 (33), 108 (10), 107 (13), 98 (15),
7 (25), 96 (24), 95 (55), 94 (18), 93 (17), 84 (27), 83 (54),
2 (25), 81 (53), 80 (11), 79 (16), 71 (19), 70 (76), 69 (60),
8 (25), 67 (45), 57 (23), 56 (40), 55 (100), 53 (11), 43
4
NMR yield). Purification by column chromatography on
silica gel (pentane/ether¼6:4) gave 90 mg (64%) of 3 (96%
purity determined by GC). The following spectral and analyt-
ical data were obtained from 1:1.3 mixture of diastereomers.
IR (NaCl): 3354, 2956, 2873, 1639, 1450, 1435, 1419, 1344,
(
17), 41 (40); HRMS calcd for C H O: 238.2297, found:
16 30
2
Found: C, 80.50; H, 12.85.
38.2294. Anal. Calcd for C H O: C, 80.61; H, 12.68.
16 30
ꢁ
1 1
1301, 1027, 996, 910 cm ; H NMR (400 MHz, CDCl ):
3
d 5.87–5.69 (m, 1H), 5.09–4.95 (m, 2H), 4.00–3.91 (m,
1H), 2.32–2.16 (m, 0.6H), 2.07–1.99 (m, 0.4H), 1.93–1.50
(m, 6H), 1.31–1.20 (m, 2H), 1.08–1.04 (m, 1.2H), 1.02–
4.2.3. 2,4-Dimethyl-5-pentene-2-ol (1c). This reaction was
carried out on a 3.0 mmol scale. Purification by column chro-
1
3
matography on silica gel (pentane/ether¼6:4) gave 78 mg
0.98 (m, 0.8H); C NMR (100 MHz, CDCl ) (major and
3
(
3
20%) of 1c (97% purity determined by GC). IR (NaCl):
404, 2970, 2926, 1640, 1456, 1378, 1159, 908 cm ; H
minor): d (142.4, 144.4), (113.76, 113.75), (76.7, 77.5),
(53.6, 53.5), (40.1, 42.7), (35.5, 34.5), (27.7, 28.9), (22.4,
21.8), (18.3, 18.6) (t, J¼19.3 Hz); MS (CI) m/z (relative in-
tensity, %): 142 (M+1, 16), 125 (10), 124 (100), 123 (4), 82
(5), 67 (2); HRMS (CI) calcd for C H DO (M+1):
ꢁ
1 1
NMR (400 MHz, CDCl ): d 5.81 (ddd, J¼8.8 Hz, 10.0 Hz,
3
1
7.2 Hz, 1H), 5.09–4.94 (m, 2H), 2.50–2.39 (m, 1H), 1.74
s, 1H), 1.60 (dd, J¼9.6 Hz, 14.2 Hz, 1H), 1.49 (dd,
J¼4.0 Hz, 14.2 Hz 1H), 1.24 (s, 3H), 1.20 (s, 3H), 1.03 (d,
(
9
16
142.1263, found: 142.1337.
1
3
J¼6.8 Hz, 3H); C NMR (100 MHz, CDCl ): d 146.2,
3
113.2, 71.5, 50.1, 35.2, 30.4, 29.4, 22.7; MS (CI) m/z (relative
intensity, %): 129 (M+1, 0.8), 112 (9), 111 (100), 95 (1), 69
4.4. trans-4-Vinyl-hexahydro-cyclopenta[b]pyran-2-one
(5)
(
4); HRMS (CI) calcd for C H O (M+1): 129.1201, found:
8 17
1
29.1277.
To a mixture of cyclopentene oxide (85.1 mg, 1.01 mmol)
and NiCl (PPh ) (19.6 mg, 0.03 mmol) was added vinyl
magnesium chloride (1.30 M in THF, 1.7 mL, 2.2 mmol)
2
3 2
4
.2.4. 4-Methyl-5-hexen-1-ol (1d). Purification by column
ꢀ
chromatography on silica gel (pentane/ether¼6:4) gave
0 mg (62%) of 1d (96% purity determined by GC). IR
NaCl): 3324, 3077, 2936, 1640, 1420, 1374, 1058, 910,
at 25 C. After stirring for 3 h, CO was added to the solu-
2
7
(
tion. After stirring for 30 min, aqueous 3 N HCl (2 mL) was
added to the solution and the mixture was stirred for 2 h at
ꢁ
1
1
ꢀ
Na SO and evaporated to give an orange crude product.
6
82 cm
;
H NMR (400 MHz, CDCl ): d 5.69 (ddd,
3
40 C. The product was extracted with ether, dried over
J¼7.2 Hz, 10.1 Hz, 17.2 Hz, 1H), 4.99–4.92 (m, 2H), 3.64
t, J¼7.2 Hz, 2H), 2.14 (qtd, J¼7.2 Hz, 7.2 Hz, 7.2 Hz,
H), 1.62–1.51 (m, 2H), 1.40–1.31 (m, 3H), 1.00 (d,
2
4
(
1
The NMR and GC analyses of the crude mixture indicated
the formation of 5 (95% purity determined by GC) as
1:1.3 mixture of diastereomers. Purification by HPLC
afforded 62 mg (37%) of 5 as a mixture of diastereomers
with ca. 1:5 ratio due to the loss of the minor isomer. Major
diastereomers. IR (NaCl): 3436, 2957, 2874, 1732, 1640,
1
3
J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl ): d 144.2,
3
1
12.7, 63.1, 37.7, 32.7, 30.6, 20.4; MS (EI) m/z (relative in-
+
tensity, %): 114 (M , 0.1), 113 (0.1), 96 (9), 95 (6), 83 (12),
2 (8), 81 (100), 71 (27), 70 (86), 69 (15), 68 (77), 67 (30), 58
8
ꢁ
1 1
(
(
11), 57 (27), 56 (22), 55 (95), 54 (17), 53 (19), 42 (14), 41
37), 39 (20); HRMS calcd for C H O: 114.1045, found:
1438, 1418, 1256, 1187, 918 cm ; H NMR (400 MHz,
CDCl ): d 5.67 (ddd, J¼7.2 Hz, 10.0 Hz, 17.2 Hz, 1H),
7
14
3
114.1042. Anal. Calcd for C H O: C, 73.63; H, 12.36.
7
Found: C, 73.35; H, 12.08.
5.10–5.03 (m, 2H), 4.10 (td, J¼10.2 Hz, 7.6 Hz, 1H),
14
2.89–2.81 (m, 1H), 2.44–2.35 (m, 2H), 2.18–2.10 (m,
1H), 1.96–1.60 (m, 4H), 1.29–1.20 (m, 2H); C NMR
(100 MHz, CDCl ): d 171.6, 139.1, 115.2, 84.0, 46.1,
1
3
4
.2.5. 2,2,4-Trimethyl-5-hexen-1-ol (1e). Purification by
3
column chromatography on silica gel (pentane/ether¼7:3)
gave 70 mg (50%) of 1e (98% purity determined by GC).
IR (NaCl): 3334, 2955, 2244, 1643, 1456, 1365, 1040,
41.5, 35.3, 29.2, 25.0, 19.3; MS (EI) m/z (relative intensity,
%): 166 (M , 5), 138 (10), 124 (28), 95 (26), 82 (16), 81
+
(18), 80 (100), 79 (31), 68 (10), 67 (21), 54 (11), 53 (10),
41 (10); HRMS (EI) calcd for C H O : 166.0994, found:
166.0995. Anal. Calcd for C H O : C, 72.26; H, 8.49.
ꢁ
; H NMR (400 MHz, CDCl ): d 5.69 (ddd,
3
1
1
9
08 cm
J¼8.6 Hz, 10.3 Hz, 17.2 Hz, 1H), 5.02–4.87 (m, 2H), 3.36
d, J¼11.0 Hz, 1H), 3.28 (d, J¼11.0 Hz, 1H), 2.35–2.25
10 14 2
1
0 14 2
(
Found: C, 72.35; H, 8.65.

6640
Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
+
4
.5. General procedure for nickel-catalyzed 2:2 coupling
reaction of vinyl Grignard reagents with chlorosilanes
Table 2)
(relative intensity, %) 448 (M , 4), 259 (3), 236 (5), 199 (5),
198 (20), 197 (100), 181 (3), 174 (10), 165 (2), 158 (2), 119
(2), 105 (5); HRMS calcd for C H Si : 448.2043, found:
(
3
0
32
2
448.2047. Anal. Calcd for C H Si : C, 80.30; H, 7.19.
30 32 2
Found: C, 80.14; H, 7.21.
To a mixture of chlorosilanes (1.0 mmol) and NiCl (PPh )
2
3 2
(
(
19.6 mg, 0.03 mmol) was added vinyl magnesium chloride
ꢀ
1.30 M in THF, 1.2 mL, 1.5 mmol) at 25 C. After stirring
4.5.5. 1,4-Bis(triphenylsilyl)-2-butene (6e). Purification by
recrystallization with chloroform/hexane afforded 211 mg
(79%) of 6e. IR (KBr): 3065, 3009, 2486, 1427, 1397,
for 3 h, aqueous 1 N HCl was added and the products were
extracted with ether. The organic layer was dried over
MgSO and evaporated to give crude products. Purification
by HPLC or recrystallization afforded the corresponding
products (6a–6e).
ꢁ1
1172, 1112, 1063, 998, 966, 766, 732, 700, 517, 478 cm ;
H NMR (400 MHz, CDCl ): d 7.52–7.25 (m, 30H), 5.49–
3
4
1
1
3
5.41 (m, 2H), 2.28–2.06 (m, 4H); C NMR (100 MHz,
CDCl ): (trans isomer) d 135.5, 134.7, 129.2, 127.6, 125.1,
3
4.5.1. 1,4-Bis(tributylsilyl)-2-butene (6a). Purification by
HPLC with CHCl as eluent afforded 150.2 mg (66%) of
19.6; (cis isomer) d 135.5, 134.7, 129.3, 127.6, 123.8, 14.6;
MS (EI) m/z (relative intensity, %) 572 (M , 3), 261 (6),
+
3
6
2
7
2
a (98% purity determined by GC). IR (NaCl): 2957, 2921,
260 (24), 259 (100), 236 (2), 181 (6), 180 (2), 105 (2);
HRMS calcd for C H Si : 572.2356, found: 572.2352.
Anal. Calcd for C H Si : C, 83.86; H, 6.33. Found: C,
40 36 2
872, 2857, 1464, 1376, 1194, 1082, 886, 789, 762,
28 cm ; H NMR (400 MHz, CDCl ): d 5.29–5.18 (m,
H), 1.43–1.39 (m, 4H), 1.36–1.22 (m, 24H), 0.88 (t,
4
0
36
2
ꢁ1 1
3
83.59; H, 6.13.
1
3
J¼6.8 Hz, 18H), 0.54–0.47 (m, 12H); C NMR (100 MHz,
CDCl ): (trans isomer) d 124.5, 26.8, 26.1, 18.4, 13.8, 11.9;
3
4.6. 1,4-Bis(tributylsilyl)-1,4-diphenyl-2-butene (7)
(
cis isomer) d 123.2, 26.8, 26.2, 13.8, 13.6, 12.2; MS (EI)
+
m/z (relative intensity, %) 452 (M , 11), 199 (94), 143
100), 101 (12), 87 (13), 59 (14); HRMS calcd for
C H Si : 452.4233, found: 452.4224. Anal. Calcd for
To a mixture of chlorotributylsilane (235 mg, 1.00 mmol)
and NiCl (PPh ) (19 mg, 0.03 mmol) was added a THF
solution of b-phenyl vinyl magnesium bromide (0.52 M in
(
2
3 2
2
8
60
2
ꢀ
C H Si : C, 74.25; H, 13.35. Found: C, 74.26; H, 13.07.
2
THF, 2.9 mL, 1.5 mmol) at 25 C under nitrogen. After
8
60
2
stirring for 3 h, similar workup as mentioned above afforded
yellow crude products (88% NMR yield). Purification by
HPLC with CHCl as an eluent afforded 215 mg (71%) of
4
.5.2. 1,4-Bis(tripropylsilyl)-2-butene (6b) [CAS Registry
Number 349152-14-3]. Purification by HPLC with CHCl3
as eluent afforded 126.3 mg (69%) of 6b (99% purity deter-
mined by GC). Spectroscopic data were in agreement with
3
7. IR (NaCl): 2956, 2922, 2871, 2857, 1464, 1081, 886,
764, 744, 700 cm ; H NMR (400 MHz, CDCl ): d 7.23–
ꢁ
1 1
3
5
1
those of previously published material.
(
H
400 MHz, CDCl ): (trans isomer) d 5.21–5.18 (m, 2H),
NMR
7.02 (m, 10H), 5.88–5.74 (m, 2H), 3.38–3.01 (m, 2H), 1.30–
1.01 (m, 24H), 0.88–0.68 (m, 18H), 0.55–0.33 (m, 12H);
3
1
3
1
.41–1.40 (m, 4H), 1.38–1.28 (m, 12H), 0.97–0.91 (t,
C NMR (100 MHz, CDCl ): (trans isomer) d 143.2, 128.4,
3
J¼7.2 Hz, 18H), 0.54–0.49 (m, 12H); (cis isomer) d 5.28–
127.9, 127.2, 124.1, 40.6, 27.0, 26.1, 13.9, 11.3; (cis isomer)
d 143.1, 128.0, 127.0, 126.6, 124.0, 35.5, 26.9, 26.1, 13.8,
11.1; MS (EI) m/z (relative intensity, %) 604 (M , 3), 348
5
0
.15 (m, 2H), 1.45–1.40 (m, 4H), 1.38–1.28 (m, 12H),
C
1
3
+
.97–0.91 (t, J¼7.2 Hz, 18H), 0.54–0.49 (m, 12H);
NMR (100 MHz, CDCl ): (trans isomer) d 124.1, 18.5,
3
(5), 291 (2), 199 (100), 143 (92), 87 (22), 59 (29); HRMS
calcd for C H Si : 604.4859, found: 604.4868. Anal. Calcd
for C H Si : C, 79.39; H, 11.33. Found: C, 79.21; H, 11.13.
1
8.4, 17.3, 15.0; (cis isomer) d 122.8, 18.6, 18.5, 17.4, 15.1.
4
0
68
2
4
0
68
2
4.5.3. 1,4-Bis(triethylsilyl)-2-butene (6c). Purification by
HPLC with CHCl as eluent afforded 83 mg (58%) of 6c
4.7. N-(2-Methyl-1-phenyl-3-butenyl)phenylamine (18)
[CAS Registry Number 80188-13-2]
3
(
99% purity determined by GC). IR (NaCl): 2952, 2874,
ꢁ
1
1
1464, 1417, 1238, 1154, 1016, 812, 751, 722 cm ; H
NMR (400 MHz, CDCl ): d 5.29–5.21 (m, 2H), 1.45–1.42
Vinyl magnesium chloride (1.30 M in THF, 1.5 mL,
2.0 mmol) was added to NiCl (PPh )
3
1
3
(
NMR (100 MHz, CDCl ): (trans isomer) d 124.4, 17.3, 7.4,
m, 4H), 0.96–0.91 (m, 18H), 0.56–0.48 (m, 12H);
C
(19.6 mg,
0.03 mmol) at 25 C. After stirring for 3 h, benzylideneani-
line (181.2 mg, 1.00 mmol) was added to the solution at
2
3 2
ꢀ
3
3
intensity, %): 284 (M , 15), 140 (11), 117 (4), 116 (12), 115
.2; (cis isomer) d 123.1, 12.6, 7.4, 3.3; MS (EI) m/z (relative
+
ꢀ
ꢁ78 C. After stirring for 30 min, the solution was warmed
ꢀ
uct was extracted with ether, dried over MgSO and evapo-
ꢀ
(
(
100), 111 (9), 88 (6), 87 (69), 83 (4), 59 (19), 58 (3); HRMS
EI) calcd for C H Si : 284.2356, found: 284.2355.
to 0 C and stirred at 0 C for an additional 30 min. The prod-
1
6
36
2
4
rated to give an orange crude product. Purification by
column chromatography on silica gel (hexane/ether¼8:2)
gave 137 mg (58%) of 18 as a mixture of diastereomers
(erythro/threo¼94:6). The stereochemistries were deter-
mined by comparison of their NMR data with the reported
4
.5.4. 1,4-Bis(methyldiphenylsilyl)-2-butene (6d). Purifi-
cation by HPLC with CHCl as eluent afforded 108 mg
3
(
48%) of 6d (99% purity determined by GC). IR (NaCl):
3
8
068, 3010, 2956, 1588, 1487, 1427, 1250, 1155, 1113, 834,
04, 788, 731, 699 cm ; H NMR (400 MHz, CDCl ):
ꢁ
1
1
11
1
ones; erythro-isomer: H NMR (400 MHz, CDCl ): d
3
3
(
1
trans isomer) d 7.50–7.24 (m, 20H), 5.32–5.30 (m, 2H),
.96–1.94 (m, 4H), 0.40 (s, 6H); (cis isomer) d 7.50–7.24
m, 20H), 5.38–5.35 (m, 2H), 1.89 (d, J¼6.3 Hz, 4H), 0.51
7.36–7.20 (m, 5H), 7.06–7.02 (m, 2H), 6.62–6.58 (m, 1H),
6.46 (d, J¼7.8 Hz, 2H), 5.75 (ddd, J¼7.6 Hz, 10.1 Hz,
17.5 Hz, 1H), 5.20–5.15 (m, 2H), 4.22 (br, 1H), 4.07 (d,
J¼7.1 Hz, 1H), 2.56–2.47 (m, 1H), 1.01 (d, J¼6.8 Hz, 3H);
(
(
1
3
s, 6H); C NMR (100 MHz, CDCl ): (trans isomer)
3
1
3
d 136.9, 134.5, 129.1, 127.7, 124.8, 20.3, ꢁ4.9; (cis isomer)
C NMR (100 MHz, CDCl ): d 147.6, 142.6, 140.5, 129.0,
3
d 136.9, 134.5, 129.2, 127.8, 123.5, 15.4, ꢁ4.6; MS (EI) m/z
128.3, 127.2, 127.0, 117.1, 116.2, 113.3, 62.3, 45.2, 17.3.

Y. Fujii et al. / Tetrahedron 63 (2007) 6635–6641
6641
References and notes
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27, 3656.
1
4
. The reaction of trans-cyclododecene oxide with Grignard
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1
. (a) Grignard, V. Ann. Chim. 1901, 24, 433; (b)
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2
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5
. Watabe, H.; Terao, J.; Kambe, N. Org. Lett. 2001, 3, 1733.
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6
7
144; (h) Fouquet, G.; Schlosser, M. Angew. Chem., Int. Ed.
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8
. Sell, M. S.; Xiong, H.; Rieke, R. D. Tetrahedron Lett. 1993,
3
2
. (a) Terao, J.; Kambe, N. Bull. Chem. Soc. Jpn. 2006, 79, 663; (b)
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9
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H. J. Org. Chem. 1991, 56, 3109.
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1
0. Sell, M. S.; Klein, W. R.; Rieke, R. D. J. Org. Chem. 1995,
0, 1077.
1. Andrade, C. K. Z.; Azevedo, N. R.; Oliveira, G. R. Synthesis
002, 928.
6
1
2
3
75; (g) Terao, J.; Kambe, N. Chem. Rec. 2007, 7, 57.