Selective mono- and di-allylation and allenylation of chlorosilanes using indium

Article abstract of DOI:10.1016/j.jorganchem.2008.08.028

Allyl and allenyl groups have been introduced into silicon systems by the allylation and allenylation of chlorosilanes using allyl bromide or propargyl bromide with indium. The allylation of chlorosilanes afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. By applying this method, the reactions of 1-bromo-3-methylbut-2-ene, 3-bromo-2-methylprop-1-ene and 3-bromobut-1-ene with chlorosilanes also proceed smoothly to give regioselectively allylic rearrangement products in good yields. Mediated by indium, dichlorosilanes (R₂SiCl₂) and trichlorosilanes (RSiCl₃) can either afford monoallylated silanes or diallylated silanes depending on the amount of allyl bromide and indium used.

Full text of DOI:10.1016/j.jorganchem.2008.08.028

Journal of Organometallic Chemistry 693 (2008) 3771–3779
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Selective mono- and di-allylation and allenylation of chlorosilanes using indium
*
Zhifang Li, Chenjun Yang, Hongfang Zheng, Huayu Qiu, Guoqiao Lai
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 June 2008
Received in revised form 12 August 2008
Accepted 19 August 2008
Available online 28 August 2008
Allyl and allenyl groups have been introduced into silicon systems by the allylation and allenylation of
chlorosilanes using allyl bromide or propargyl bromide with indium. The allylation of chlorosilanes affor-
ded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. By applying this method, the reactions
of 1-bromo-3-methylbut-2-ene, 3-bromo-2-methylprop-1-ene and 3-bromobut-1-ene with chlorosil-
anes also proceed smoothly to give regioselectively allylic rearrangement products in good yields. Med-
iated by indium, dichlorosilanes (R2SiCl2) and trichlorosilanes (RSiCl3) can either afford monoallylated
silanes or diallylated silanes depending on the amount of allyl bromide and indium used.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords:
Allylation
Indium
Alkenyl groups
Chlorosilanes
1. Introduction
2. Results and discussion
Allylsilanes have become a commonly used class of organosil-
icon reagents as applied to organic synthesis. Hydrolysis and dehy-
dration of di- and tri-chloroallylsilanes yield polysiloxanes which
retain the unsaturated groups, permitting additional polymeriza-
tion across the double bonds to synthesize the functional polymers
[1]. A variety of methods have been used for the preparation of
allylsilanes. Among them, the reactions of allylic Grignard reagents
with chlorosilanes and alkoxysilanes offer a convenient route to
the synthesis of various industrial useful organosilicon com-
pounds. However, only moderate yields of the products could be
obtained in the preparation of allylic chlorosilanes with this meth-
od [2]. Allyltrichlorosilane can be prepared readily using Cu medi-
ated reaction of allyl chloride with trichlorosilane [3]. Sakurai
reported the selective allylation of polychlorosilanes by an organo-
zinc procedure [4]. Recently, some modified approaches have been
reported for the synthesis of unsaturated organosilicon com-
pounds, such as hydrosilylation and silylmetallation and/or carbo-
silylation of alkynes or hydrometallation and hydrogenation of
alkynylsilanes [5,6]. These methods are useful for the preparation
of novel and well-known silicon-containing alkenes, but it did
not work well for synthesis of unsaturated chlorosilanes [7,8].
We previously found that allylsamarium bromide was a versatile
reagent for the allylation of chlorosilanes with allyl bromide, but
when RCH@CHCH2Br or 3-bromoprop-1-yne was used, this meth-
od failed [9]. Herein we reported the organoindium mediated
selective mono- and di-allylation and allenylation of chlorosilanes
into allylsilanes and allenylsilanes.
2.1. Indium induced allylation of chlorosilanes (R3SiCl)
with allyl bromide
The reactions of various trisubstituted chlorosilanes (R3SiCl)
with allyl bromide were carried out in the presence of indium in
DMF at room temperature. After stirring for several hours, the reac-
tion mixture was quenched with 0.1 M hydrochloric acid and ex-
tracted with diethyl ether. The ether was evaporated and purified
by column chromatography to give the corresponding allylsilanes
in good yields. The products were identified by comparing their
IR, NMR, MS spectra. The results are summarized in Table 1.
When chlorodiphenylsilane was treated with allyl bromide in
the presence of indium powder in DMF or DMI (1,3-dimethylimi-
dazolidine) at room temperature, allyldiphenylsilane was obtained
in 98% and 82% isolated yields, respectively. When the reaction was
performed in THF under the similar reaction conditions, no reaction
took place (Scheme 1). The chlorodiphenylsilane, indium and allyl
bromide were used in a ratio of 1:1:1.5. The aliphatic chlorosilane
such as chlorotrimethylsilane also reacted with allyl bromide giving
the corresponding allyltrimethylsilane (3e) in good yield (entry 5).
The reactions of 1-bromo-3-methylbut-2-ene, 3-bromo-2-methyl-
prop-1-ene and 3-bromobut-1-ene with chlorodiphenylsilane also
proceed smoothly to give the corresponding allylation products in
good yields (entries 6–8). Noteworthy is that the products of the
allylic rearrangement were obtained regioselectively exclusively.
Thus, the reactions gave (2-methylbut-3-en-2-yl)-diphenylsilane
(3f), (2-methylallyl)diphenylsilane (3g) and (E)-but-2-enyldiphe-
nylsilane (3h), respectively, but no (3-methylbut-2-enyl)diphe-
nylsilane, (2-methylallyl)diphenylsilane or but-3-en-2-yldiphenyl
silane was detected in the products. When a mixture of 3-bromocy-
* Corresponding author. Tel.: +86 571 28868081; fax: +86 571 28865135.
E-mail address: gqlai@hznu.edu.cn (G. Lai).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.08.028

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Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
Table 1
Table 2
Allylation of trisubstituted chlorosilanes (R3SiCl)a
Diallylation of organodichlorosilanes (R2SiCl2) with allyl bromidesa
R1
Entry Allyl bromide
Substrate Product
Yieldsb
(%)
R1 R2
R4
R3
R4
R4
In ( 2 mmol)
DMF, r.t. 3h
+
R2SiCl 2
R2
Br
R2Si
R1
1
Ph2HSiCl
98
3a
3b
Br
Ph2HS i
2a
R3
2 (3 mmol)
R3
4 (1 mmol)
R2
2
3
4
5
6
2a
2a
2a
2a
Ph3SiCl
97
98
87
78
96
5
Ph3Si
3c
3d
Ph2MeSiCl
Ph2MeSi
PhMe2SiCl
Entry
1
Ally bromide
R2SiCl2
Product
Yieldsb (%)
98
Me2PhSi
2a
PhMeSiCl2
Me3SiCl
3e
Me3Si
Br
Me
Ph2HSiCl
Si
3f
2b
Ph2 HS i
Ph
5a
5b
3g
Ph2HS i
7
8
Ph2HSiCl
Ph2HSiCl
94
Br
Br
Ph
2c
2d
2
2a
Ph2SiCl2
99
Si
93c
Ph
3h
Ph2HS i
Br
SiHP h2
9
Ph2HSiCl
Ph2HSiCl
92
94
3i
Ph
3
4
5
2a
2a
2a
PhHSiCl2
94
91
92
Si
2e
H
5c
SiHPh2
Br
10
3j
2f
Me
Me2SiCl2
Si
a
Me
Unless otherwise noted, chlorosilanes (1 mmol) were allowed to react with In
5d
(1 mmol) and allyl bromide (1.5 mmol) in DMF at room temperature for 3 h.
b
Isolated yields based on chlorosilane used.
c
Me
Si
Z/E = 5/94.
n-BuMeSiCl2
n
-Bu
5e
SiHPh2
In
r.t.
Br
Ph2HSiCl
+
2a
3a
1
Me
Ph
6
2b
MePhSiCl2
92
Si
THF
0
5f
98%
82%
DMF
DMI
Me
Ph
Scheme 1.
7
8
2c
2d
2e
MePhSiCl2
MePhSiCl2
MePhSiCl2
88
87c
82
Si
Si
Si
5g
clohex-1-ene and chlorodiphenylsilane were treated with 1 equiv.
of indium powder in DMF for 3 h, cyclohex-2-enyldiphenylsilane
(3i) was obtained in 92% isolated yield (entry 9).
Ph
Me
2.2. Indium induced allylation of organodichlorosilanes (R2SiCl2) with
allyl bromide
5h
Unsaturated chlorosilanes, in which the aryl and aralkyl groups
are directly linked with silicon, were widely used in the prepara-
tion of functional polysiloxanes with good thermal stability and a
rapid cure [10]. The syntheses of unsaturated chlorosilanes was
first reported by Hurd [11]. Pure aryl or aralkyl allyldichlorosilanes
were prepared from allyl- and vinyltrichlorosilane and the appro-
priate Grignard reagent [12]. However, in most reactions carried
out between Grignard reagent and chlorosilanes to form partially
substituted arylchlorosilanes, successive substitution products
were always formed [13]. In our studies for the construction of
Si–C bond, we found that the substitution reaction between organ-
odichlorosilanes (R2SiCl2) and allyl bromide could be controlled at
the desired mono- or di- substituted manner. When dichlorosil-
anes (R2SiCl2), indium and allyl bromide were used in a ratio of
1:2:3, the diallyl substituted organosilicons (5) were obtained in
excellent yields. Noteworthy is the fact that the diallylation of
dichlorosilanes (R2SiCl2) were generally clean and no mono-allylat-
ed products could be detected by GC–MS spectra of the crude prod-
ucts. The results are listed in Table 2.
Ph
9
Me
5i
a
Unless otherwise noted, chlorosilanes (1 mmol) were allowed to react with In
(2 mmol) and allyl bromide (3 mmol) in DMF at room temperature for 3 h.
b
Isolated yields based on 4.
Z/E = 4/95.
c
While dichloro(methyl)phenylsilane (MePhSiCl2), indium and
allyl bromide were used in a ratio of 1:1:1.5, a mixture of mono-
and di-allylated products, diallyl(methyl)(phenyl)silane (5a, 33%)
and allylchloro(methyl)phenylsilane (6a, 35%) were detected.
Me
Ph
Me
+
DMF (2 mL)
r.t.
Br
Si
Cl
Si
Ph
MePhSiCl2
+
ð1Þ
2a (1.5 mmol)
4 (1 mmol)
5a
6a
33%
35%

Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
3773
Table 4
Monoallylation of organotrichlorosilanes (RSiCl3) with allyl bromidea
Table 3
Monoallylation of organodichlorosilanes (R2SiCl2) with allyl bromidea
Entry
1
Ally bromide
RSiCl3
Product
Yieldsb (%)
92
R1
R1 R2
R4
R3
2a
PhSiCl3
R4
Ph
Si
In (10 mmol)
DMI, 70oC, 3h
+
R
2SiCl2
R2
Br
R2Si
Cl
R3
2 (15 mmol)
8a
6
Cl
Me
Si
4 (10 mmol)
Entry
1
Ally bromide
R2SiCl2
Product
Yieldsb (%)
2
3
2a
2b
MeSiCl3
PhSiCl3
91
87
Cl
2a
PhMeSiCl2
6a (92), 5a (7)
8b
8c
Me
Ph
Si
Si
Ph
Cl
Ph
2
3
4
5
6
7
8
2a
2a
2a
2a
2b
2c
2d
2e
Ph2SiCl2
6b (96), 5b (3)
6c (94), 5c (4)
6d (90), 5d (8)
6e (90), 5e (7)
6f (81), 5f (10)
6g (89), 5g (8)
6h (91c), 5h (5)
6i (89), 5i (9)
Cl
Si
Cl
Ph
Ph
Si
Ph
4
2c
PhSiCl3
PhSiCl3
87
PhHSiCl2
Si
Cl
H
Cl
8d
Me
Me2SiCl2
Ph
Si
Cl
Me
5
2d
89c
Si
Cl
Me
Si
8e
n-BuMeSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
n
-Bu
Cl
a
Chlorosilanes (10 mmol) were allowed to react with In (20 mmol) and allyl
bromide (30 mmol) in DMI at 70 °C for3 h.
b
Me
Ph
Isolated yields based on RSiCl3 used.
Z/E = 4/95.
c
Si
Si
Cl
Cl
Me
Ph
R
Si
In (20 mmol)
Br
Ph
RSiCl3
+
Si
Si
DMI , 70º, 3h
Cl
Me
Cl
Cl
(10 mmol)
R = Me, Ph
(30 mmol)
8
Ph
9
Me
Scheme 2.
a
Unless otherwise noted, chlorosilanes (10 mmol) were allowed to react with In
(10 mmol) and allyl bromide (15 mmol) in DMI at 70 °C for 3 h.
b
Isolated yields based on 4.
Z/E = 5/93.
2.3. Indium induced allylation of organotrichlorosilanes (RSiCl3) with
allyl bromide
c
With the success for the synthesis of allyl substituted organo-
silanes and chlorosilanes, we subsequently investigated the ally-
lation of trichlorosilanes (RSiCl3) with allylindium bromide.
When trichlorophenylsilane (10 mmol) and indium powder
(20 mmol) were treated with allyl bromide (30 mmol), the dial-
lylchlorophenylsilane was obtained in high yield (92%) (Scheme
2). Under similar reaction conditions, trichloromethylsilane also
reacted with allylindium bromide smoothly, giving the corre-
sponding products in good yields. The results are summarized
in Table 4.
When the similar reaction was performed in DMI at room tem-
perature for 12 h, 6a was obtained in 11% isolated yield and only
trace amount of gem-allylated product 5a could be detected in
the 1H NMR spectra of the crude product. When the reaction
temperature was increased from room temperature to 70 °C,
allylchloro(methyl)phenylsilane (6a) was obtained in good yield
(Eq. (2))
2.4. The reaction of trisubstituted chlorosilanes (R3SiCl) with propargyl
bromide
Me
Ph
Me
+
DMI (2 mL)
70oC
Br
Si
Cl
Si
Ph
MePhSiCl2
+
ð2Þ
2a (1.5 mmol)
4 (1 mmol)
5a
6a
Functional allenes such as allenylsilanes have proved to be ex-
tremely versatile, key intermediates in modern organic synthesis
[14]. Regioselective reactions of propargyl and allenyl organome-
tallics with chlorosilanes provide a convenient route for the syn-
thesis of these compounds. However, these organometallics often
exist as an equilibrium mixture [14a]. We found that organoin-
dium was a useful reagent for the regioselective allenylation of
chlorosilanes. When 3-bromoprop-1-yne (1.5 mmol) and chlorodi-
phenylsilane (1 mmol) were treated with 1 equiv. of indium
7%
92%
On the basis of the results obtained with simple dichlorometh-
ylphenylsilane, it seemed logical to investigate the possibility of
extending this methodology to the controlled monoallylation of
various organodichlorosilanes. The results and the scope of this
reaction are summarized in Table 3, which clearly indicates that
the present strategy affords a general protocol for the synthesis
of allyl substituted chlorosilanes.

3774
Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
Table 5
Monoallenylation of trisubstituted chlorosilanes (R3SiCl)a
Entry
1
Propargyl bromide
Substrate
Ph2HSiCl
Product
Yieldsb(%)
95
C
9a
10a
10b
Ph2HSi
Ph 3 Si
Br
C
2
9a
9a
9a
9a
9a
Ph3SiCl
98
98
96
94
81
97
98
94
79
93
C
3
Ph2MeSiCl
PhMe2SiCl
VinylMe2SiCl
Me3SiCl
10c
10d
10e
10f
10g
10h
10i
10k
10j
Ph 2 MeS i
PhMe2Si
VinylMe2 Si
Me3Si
C
4
C
5
C
6
C
7
Ph2HSiCl
Ph3SiCl
Br
9b
Ph 2 HS i
Ph3Si
C
C
8
9b
9b
9b
C
9
Ph2MeSiCl
Me3SiCl
Ph2MeS i
Me3Si
10
C
11
Ph2HSiCl
Ph2HS i
9c
Br
a
Unless otherwise noted, chlorosilanes (1 mmol) were allowed to react with In (1 mmol) and propargyl bromide (1.5 mmol) in DMF at room temperature for 3 h.
Isolated yields based on 1.
b
ylsilane ane chlorotrimethylsilane, the regioselective products
DMF
R2
Br
R1
R3Si
R2
were obtained in good yields, respectively (entries 8–10). When
3-bromobut-1-yne and chlorodiphenylsilane were used as the sub-
strates, the buta-1,2-dienyldiphenylsilane was produced in an
excellent yield (entry 11) (see Table 5 and Scheme 3).
R3SiCl
R1
In
C
r.t., 3h
9(1.5mmol)
1(1mmol)
Scheme 3.
1mmol
10
2.5. The reaction of disubstituted chlorosilanes (R2SiCl2) with
propargyl bromide
powder in DMF for 3 h at room temperature to give allenyldiphe-
nylsilane (10a) in 95% isolated yield (entry 1). When under the
similar reaction conditions, 1-bromobut-2-yne was treated with
chlorodiphenylsilane, chlorotriphenylsilane, chlorodiphenylmeth-
On the basis of the results obtained with the monoallenylation
of R3SiCl, we subsequently investigated the mono- and di-allenyla-
Table 6
Diallenylation of disubstituted dichlorosilanes (R2SiCl2)a
Entry
1
Propargyl bromide
Substrate
PhMeSiCl2
Product
Yieldsb (%)
97
C
C
MePhS i
11a
11b
Br
C
2
3
4
5
9a
Ph2SiCl2
98
97
91
93
Ph2 Si
C
C
9a
9a
9a
PhHSiCl2
Me2SiCl2
n-BuMeSiCl2
11c
11d
HPhSi
C
C
Me 2 Si
n-BuMeSi
MePhSi
C
C
C
11e
11f
C
6
PhMeSiCl
PhMeSiCl2
94
97
Br
9b
C
C
7
MePhSi
11g
Br
C
9c
a
Unless otherwise noted, chlorosilanes (1 mmol) were allowed to react with In (2 mmol) and propargyl bromide (3 mmol) in DMF at room temperature for 3 h.
Isolated yields based on (R2SiCl2) 2.
b

Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
3775
Table 7
Monoallenylation of disubstituted dichlorosilanes (R2SiCl2)a
Entry
1
Propargyl bromide
Substrate
PhMeSiCl2
Product
Yieldsb(%)
C
12a (89), 11a (9)
MePhSi
Br
Cl
C
2
3
4
5
6
7
9a
Ph2SiCl2
12b (93), 11b (5)
12c (90), 11c (7)
12d (87), 11d (9)
12e (87), 11e (10)
12f (92), 11f (4)
12g (93), 11g (5)
Ph 2 Si
HPhS i
Me 2 Si
Cl
C
9a
9a
9a
PhHSiCl2
Cl
Cl
C
Me2SiCl2
C
n-BuMeSiCl2
PhMeSiCl2
PhMeSiCl2
n- Bu Me Si
Cl
C
MePhSi
Cl
Br
9b
Br
C
MePhSi
Cl
9c
a
Unless otherwise noted, chlorosilanes (10 mmol) were allowed to react with In (10 mmol) and propargyl bromide (15 mmol) in DMI at r.t. for 3 h.
Isolated yields based on 2 (R2SiCl2).
b
tion of R2SiCl2. When dichloromethylphenylsilanes (MePhSiCl2),
extracted with diethyl ether (3 ꢀ 5 mL), the diethyl ether solution
was washed with saturated NaCl (2 ꢀ 5 mL) and dried over anhy-
drous MgSO4. The solvent was removed by evaporation under re-
duced pressure. The crude product was purified by preparative
TLC on silica gel (cyclohexane as eluent).
indium and propargyl bromide were used in a ratio of 1:2:3, diall-
enylated product was obtained in 97% isolated yield. The results
and scopes are listed in Table 6.
When dichloromethylphenylsilanes (MePhSiCl2), indium and
propargyl bromide were used in a ratio of 1:1:1.5 in DMI at room
temperature, diallenylmethyl(phenyl)silane (11a, 9%) and allenyl-
chloro(methyl)(phenyl)silane (12a, 89%) was detected. Under sim-
ilar reaction conditions, a variety of allenylated chlorosilanes were
obtained in good yields (Table 7).
In conclusion, we present the novel selective allylation and
allenylation of chlorosilanes with organoindium reagents. By
applying this method, aryl and aralkyl unsaturated chlorosilanes
as well as diallyl chlorosilanes containing different allyl and allenyl
groups were prepared conveniently. The new types of allyl- and
allenyl substituted chlorosilanes prepared herein possess unsatu-
rated carbon–carbon bonds and will meet our further require-
ments to permit additional polymerization across the double
bonds so as to synthesize functional polymers.
Allyldiphenylsilane (3a) [2c] IR:
m
max (liquid film) 3069.3, 3003.1,
2972.5, 2920.0, 2125.3, 1629.8, 1427.0, 1155.0, 1114.1 cmꢁ1
;
1H
NMR (400 MHz, CDCl3): d 7.32–7.64 (10H, m, ArH), 5.79–5.89 (1H,
m, CH), 4.88–4.97 (2H, m, CH2@), 4.86 (1H, s, SiH), 2.12–2.15
(2H, d, J = 7.3 Hz, CH2CH@CH2); 13C NMR (100 MHz, CDCl3): d
135.40, 133.73, 133.57, 129.39, 127.05, 114.79, 19.77; MS: m/z
(%): 224 (M+, 2.17), 183 (100), 105 (13.62).
Allyltriphenylsilane ( 3b) [15a] IR: mmax (KBr) 3066.0, 3041.0,
2996.0, 2923.3, 2863.4, 1628.1, 1427.3, 1112.6 cmꢁ1 1H NMR
;
(400 MHz, CDCl3): d 7.34–7.53 (15H, m, ArH), 5.84–5.90 (1H, m,
CH), 4.87–4.97 (2H, d, d, J = 10.1, 15.2 Hz, CH2@), 2.38–2.40 (2H,
d, J = 7.4 Hz, CH2CH@CH2); 13C NMR (100 MHz, CDCl3): d 135.76,
134.55, 133.82, 129.56, 127.85,115.10, 21.19; MS: m/z (%): 301
(M++1, 2.21), 260 (23.58), 259 (100), 181 (9.92), 105 (3.74).
Allyldiphenylmethylsilane (3c) [15a] IR:
m
max (liquid film) 3069.6,
2924.0, 2853.5, 1630.4, 1427.6, 1251.5, 1151.9, 1112.9 cmꢁ1
;
1H
3. Experimental
NMR (400 MHz, CDCl3): d 7.32–7.36 (10H, m, ArH), 5.74–5.85 (1H,
m, CH), 4.85–4.93 (2H, d, d, J = 10.2, 15.3 Hz, CH2@), 2.06–2.08
(2H, d, J = 7.2 Hz, CH2CH@CH2), 0.55 (3H, s, CH3); 13C NMR
Tetrahydrofuran was distilled from sodium-benzophenone
immediately prior to use. DMF and DMI were distilled from GaH2
at reduced pressure. All reactions were conducted under a nitrogen
atmosphere. 1H NMR spectra were recorded on a BRUKER AV-
400 MHz instrument as CDCl3 solutions using TMS as an internal
standard. Chemical shifts (d) are reported in ppm and coupling
constants J are given in Hz. IR spectra were taken as thin films with
a BRUKER TENSOR-27 infrared spectrometer. Elemental analysis
was performed on a VARIO EL-3 instrument. Indium powder, the
starting chlorosilanes and all reagents were purchased from com-
mercial sources and were used without further purification.
(100 MHz, CDCl3):
d 136.41, 134.41, 133.92, 129.16, 127.70,
114.13, 22.03, ꢁ4.95; MS: m/z (%): 278 (M+, 4.00), 198 (27.09),
197 (100).
Allyldimethylphenylsilane (3d) [15a] IR:
2998.6, 2957.6, 2915.9, 1630.0, 1426.8, 1249.9, 1155.4,
1114.3 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.33–7.50 (5H, m,
mmax (liquid film) 3070.3,
;
ArH), 5.72–5.80 (1H, m, CH), 4.83–4.88 (2H, d, d, J = 10.1, 15.2 Hz,
CH2@), 1.74–1.76 (2H, d, J = 7.2 Hz, CH2CH@CH2), 0.27 (3H, s,
CH3); 13C NMR (100 MHz, CDCl3): d 138.46, 134.43, 133.43,
128.81, 127.64, 113.19, 23.49, ꢁ3.70; MS: m/z (%): 176 (M+,
1.00), 161 (0.88), 136 (12.52), 135 (100), 105 (2.97).
3.1. General procedure for the synthesis of allylaralkyl silanes (3a–3i)
Allyltrimethylsilane (3e) [15a]: 1HNMR (400 MHz,CDCl3): d 5.66–
5.71 (1H, m, CH), 4.77–4.83 (2H, m, CH2@), 1.74 (2H, d, J = 7.8 Hz,
CH2CH@CH2), 0.21–0.33 (9H, s, CH3); MS: m/z (%): 114 (M+, 2.56),
74 (29.04), 73(43.76), 45(100).
Allyl bromide (1.5 mmol) and indium (1 mmol) in dry DMF
(2 mL) were added to a three-necked flask with stirring at room
temperature under a nitrogen atmosphere. The mixture was stirred
for about 1 h. Chlorosilanes (1 mmol) were added dropwise. The
reaction mixture was stirred for 3 h and then was quenched with
0.1 M hydrochloric acid (2 mL). The resulting mixture was
(2-Methylbut-3-en-2-yl)diphenylsilane (3f): 1H NMR (400 MHz,
CDCl3): d 7.25–7.62(10H, m, ArH), 5.72–5.76(1H, m, CH@), 4.80
(1H, s, SiH), 4.58–4.65 (2H, m, CH2@), 1.03 (6H, s, CH3); 13C NMR

3776
Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
(100 MHz, CDCl3):
d
137.23, 134.89, 133.77, 130.21, 127.05,
2ꢀ CH2@), 4.77 (1H, s, Si–H), 2.12 (4H, d, J = 7.2 Hz,
2 ꢀ CH2CH@CH2); 13C NMR (100 MHz, CDCl3): d 134.84, 134.12,
133.55, 129.32, 127.65, 114.59, 19.85; MS: m/z (%): 188 (M+,
2.31), 147 (100).
114.63, 24.28, 3.1; MS: m/z (%): 252 (M+, 1.32), 183 (100),
175(27.8); Anal. Calc. for C17H20Si: C, 80.89; H, 7.99; Si, 11.13.
Found: C, 80.76; H, 7.78; Si, 11.25%.
(2-Methylallyl)diphenylsilane (3g): IR mmax (liquid film) 3071.2,
3013,3, 2972.2, 2925.3, 2856.3, 2127.2, 1648.2, 1435.8,
Diallyldimethylsilane (5d) [9]: 1H NMR (400 MHz, CDCl3): d5.77–
5.86 (2H, m, 2 ꢀ CH), 4.92–5.01 (4H, m, 2 ꢀ CH2@), 1.85 (4H, d,
J = 7.3 Hz, 2 ꢀ CH2CH@CH2), 0.23 (6H, s, CH3); 13C NMR
(100 MHz, CDCl3): d 133.54, 115.92, 19.85, ꢁ2.32; MS: m/z (%):
140 (M+, 0.89), 125 (54.28), 99 (100).
1111.2 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.31–7.68 (10H, m,
;
ArH), 4.80 (1H, s, SiH), 4.62 (2H, s, CH2@), 2.15 (2H, s, Si-CH2),
1.73 (3H, s, CH3); 13C NMR (100 MHz, CDCl3): d 140.21, 135.29,
134.67, 134.32, 131.12, 129.87, 115.23, 25.42, 19.28; MS: m/z
(%): 238(M+, 0.25), 223 (12.28), 183 (100); Anal. Calc. for
C16H18Si: C, 80.61; H, 7.61; Si, 11.78. Found: C, 80.52; H, 7.76; Si,
11.69%.
Diallylmethylbutylsilane (5e) [9]: 1H NMR (400 MHz, CDCl3): d
5.63–5.69 (2H, m, 2 ꢀ CH), 4.97–5.03 (4H, m, 2 ꢀ CH2@), 1.31–
1.42 (8H, m), 0.92–1.07 (2H, m, CH2CH3), 0.52–0.68 (3H, t,
CH3CH2), 0.21 (3H, s, CH3Si); 13C NMR (100 MHz, CDCl3): d
133.89, 115.13, 32.13, 30.24, 25.62, 19.76, 15.32, ꢁ2.67; MS: m/z
(%): 182 (M+, 1.34), 167 (47.36), 141 (100).
(E)-But-2-enyldiphenylsilane (3h) IR: mmax (liquid film) 3072.5,
3015.8, 2956.3, 2925.2, 2857.2, 2128.3, 1651.2, 1478.3, 1429.4,
1118.2 cmꢁ1
;
1H NMR (400 MHz, CDCl3): d 7.27–7.65 (10H, m,
Di-(2-methylbut-3-en-2-yl)methylphenylsilane ( 5f): 1H NMR
(400 MHz, CDCl3): d 7.28–7.47 (5H, m, ArH), 5.74–5.77 (2H, m,
2 ꢀ CH), 4.91–5.03 (4H, m, 2 ꢀ CH2@), 1.21 (12H, s, 4 ꢀ CH3),
0.31 (3H, s, CH3Si); 13C NMR (100 MHz, CDCl3): d 138.35, 135.02,
134.13, 130.35, 128.98 114.13, 23.67, 2.92; MS: m/z (%): 258 (M+,
1.32), 243 (10.35), 181 (100); Anal. Calc. for C17H26Si: C, 79.00;
H, 10.14; Si, 10.87. Found: C, 78.88; H, 10.82 Si, 10.79%.
ArH), 5.65–5.50 (2 H, m, CH@CH), 4.81 (1H, s, SiH), 2.13 (2H, d,
J = 6.2 Hz, Si-CH2), 1.56 (3H, d, J = 7.3 Hz, CH3); 13C NMR
(100 MHz, CDCl3):
d 135.23, 134.02, 130.22, 129.12, 124.73,
123.58, 17.23, 13.12; MS: m/z (%): 238(M+, 1.52), 223 (23.52),
183 (100); Anal. Calc. for C16H18Si: C, 80.61; H, 7.61; Si, 11.78.
Found: C, 80.55; H, 7.71; Si, 11.70%.
Cyclohex-2-enyldiphenylsilane ( 3i) [15b] IR: mmax (liquid film)
3059.1, 3014.3, 2927.9, 2857.8, 2132.0, 1653.1, 1428.4, 1118.6,
Di-(2-methylallyl)methylphenylsilane ( 5g): 1H NMR (400 MHz,
CDCl3): d 7.21–7.40 (5H, m, ArH), 4.75 (4H, s, 2 ꢀ CH2@), 2.15
(4H, s, 2 ꢀ Si-CH2), 1.72 (6H, s, 2 ꢀ CH3), 0.35 (3H, s, CH3Si); 13C
NMR (100 MHz, CDCl3): d 142.01, 134.32, 133.87, 133.15, 130.78,
129.15, 115.11, 20.23, 17.23, ꢁ2.56; MS: m/z (%): 230 (M+, 0.56),
215 (3.24), 175 (100), 120 (65.32); Anal. Calc. for C15H22Si: C,
78.19; H, 9.62; Si, 12.19. Found: C, 78.28; H, 9.54; Si, 12.26%.
Di-[(E)-but-2-enyl]methylphenylsilane (5h): 1H NMR (400 MHz,
CDCl3): d 7.28–7.55 (5H, m, ArH), 5.52–5.57 (4H, m, 2 ꢀ CH@CH),
2.16 (4H, d, J = 7.2 Hz, 2 ꢀ Si-CH2), 1.74 (6H, d, J = 7.3 Hz, CH3),
0.33 (3H, s, CH3Si); MS: m/z (%): 230 (M+, 0.77), 215 (5.76), 175
(100), 120 (58.35); Anal. Calc. for C15H22Si: C, 78.19; H, 9.62; Si,
12.19. Found: C, 78.10; H, 9.70; Si, 12.11%.
1067.9, 852.9, 728.1, 702.8 cmꢁ1 1H NMR (400 MHz, CDCl3): d
;
7.20–7.62 (10H, m, ArH), 5.70–5.54 (2H, m, CH@CH), 4.77 (1H, s,
SiH), 1.98–1.26 (7H, m); 13C NMR (100 MHz, CDCl3): d 141.38,
135.38, 134.77, 134.37, 130.26, 129.65, 128.79, 127.90, 31.32,
25.00, 23.32, 19.28; MS: m/z (%): 264(M+, 2.34), 183 (100), 105
(23.18).
But-3-en-2-yldiphenylsilane ( 3j) [15a]: 1H NMR (400 MHz,
CDCl3): d 7.26–7.63 (10H, m, ArH), 5.72–5.76 (1H, m, CH@), 4.77
(1H, s, SiH), 4.58–4.65 (2H, m, CH2@), 2.21 (1H, m, CH), 1.02 (3H,
d, J = 6.2 Hz, CH3); 13C NMR (100 MHz, CDCl3): d 137.24, 134.88,
133.77, 130.21, 127.06, 114.63, 26,32, 24.28; MS: m/z (%): 238
(M+, 2.42), 223 (22.52), 183 (100).
Di-(cyclohex-2-enyl)methylphenylsilane (5i): 1H NMR (400 MHz,
CDCl3): d 7.27–7.45 (5H, m, ArH), 5.55–5.62 (4H, m, 2 ꢀ CH@CH),
1.26–1.97 (14H, m), 0.30 (3H, s, CH3); 13C NMR (100 MHz, CDCl3):
d 142.13, 135.33, 134.22, 133.87, 130.65, 129.78, 128.67, 127.96,
31.56, 26.11, 23.35, 19.78; MS: m/z (%): 282 (M+, 5.70), 267
(19.00), 201 (100), 120 (67.23); Anal. Calc. for C19H26Si: C, 80.78;
H, 9.28; Si, 9.94. Found: C, 80.70; H, 9.33; Si, 9.88%.
3.2. General procedure for the synthesis of diallyl
substituted silanes (5a–5i)
Allylindium bromide (2 mmol) was prepared using the above
procedure. Dichlorosilanes (1 mmol) were added dropwise. The
reaction mixture was stirred for 3 h and then was quenched with
0.1 M hydrochloric acid (2 mL). The resulting mixture was ex-
tracted with diethyl ether (3 ꢀ 5 mL), the diethyl ether solution
was washed with saturated NaCl (2 ꢀ 5 mL) and dried over anhy-
drous MgSO4. The solvent was removed by evaporation under re-
duced pressure. The crude product was purified by preparative
TLC on silica gel (cyclohexane as eluent).
3.3. General procedure for the synthesis
of allyl substituted chlorosilanes (6a–6i)
Allylindium bromide (10 mmol) was prepared using the above
procedure in DMF. Dichlorosilanes (10 mmol) were added drop-
wise, and then the reaction mixture was stirred for 3 h at 70 °C.
The inorganic precipitate was filtered off and washed with dry
diethyl ether. The solvent was removed by evaporation and the
residual liquid was fractionally distilled.
Diallylmethylphenylsilane (5a) [9] IR: mmax (liquid film) 3072.5,
2971.3, 2916.2, 1630.0, 1426.9, 1252.1, 1154.2, 1113.2 cmꢁ1 1H
;
NMR (400 MHz, CDCl3): d 7.32–7.50 (5H, m, ArH), 5.73–5.79 (2H,
m, 2 ꢀ CH), 4.83–4.90 (4H, m, 2 ꢀ CH2@), 1.79–1.81 (4H, d,
J = 7.1 Hz, 2 ꢀ CH2CH@CH2), 0.28 (3H, s, CH3); 13C NMR
Allylchloromethylphenylsilane ( 6a) [9] IR: mmax (liquid film)
3071.2, 2969.5, 1630.5, 1427.8, 1256.2, 1157.0, 1118.3 cmꢁ1 1H
;
(100 MHz, CDCl3):
d
136.71, 134.05, 133.79, 129.06, 127.62,
NMR (400 MHz, CDCl3): d 7.25–7.45 (5H, m, ArH), 5.66–5.71 (1H,
m, CH), 4.77–4.83 (2H, m, CH2@), 1.73–1.75 (2H, d, J = 7.2 Hz,
CH2CH@CH2), 0.21–0.33 (3H, s, CH3); 13C NMR (100 MHz, CDCl3):
d 133.7, 133.2, 133.16, 129.36, 127.54, 113.73, 21.43, ꢁ1.62; MS:
m/z (%): 161 (100), 155 (21.83), 121 (37.22), 105 (14.01).
113.73, 21.44, ꢁ5.98; MS: m/z (%): 202 (M+, 2.1), 161 (100), 121
(30.5), 105 (11.9).
Diallyldiphenylsilane ( 5b) [9] IR: mmax (liquid film) 3069.6,
2998.2, 1629.9, 1427.9, 1110.8, 907.9, 732.7 cmꢁ1
;
1H NMR
(400 MHz, CDCl3): d
7.32–7.52 (10H, m, ArH), 5.78 (2H, m,
Allylchlorodiphenylsilane (6b) [9] IR: mmax (liquid film) 3069.9,
2 ꢀ CH), 4.86–4.94 (4H, t, 2 ꢀ CH2@), 2.11–2.13 (4H, d, J = 7.2 Hz,
2 ꢀ CH2CH@CH2); 13C NMR (100 MHz, CDCl3): d 134.84, 134.12,
133.55, 129.32, 127.65, 114.59, 19.85; MS: m/z (%): 264 (M+,
6.96), 223 (100), 183 (27.66), 145 (32.05).
3023.2, 2919.9,1630.0,1590.6,1428.0,1117.5 cmꢁ1
;
1H NMR
(400 MHz, CDCl3): d 7.26–7.57 (10H, m, ArH), 5.80–5.89 (1H, m,
CH), 4.88–5.01 (2H, m, CH2@), 2.18–2.22 (2H, d, J = 7.1 Hz,
CH2CH@CH2); 13C NMR (100 MHz, CDCl3):
d 133.79, 130.27,
Diallylphenylsilane (5c) [9]: 1H NMR (400 MHz, CDCl3): d 7.31–
7.51 (5H, m, ArH), 5.75–5.79 (2H, m, 2 ꢀ CH), 4.86–4.94 (4H, m,
130.05, 129.32, 127.56, 114.60, 19.83; MS: m/z (%): 258 (M+,
2.54), 217 (100), 181 (13.60).

Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
3777
Allylchlorophenylsilane (6c) [15c]: 1H NMR (400 MHz, CDCl3): d
7.35–7.68 (5H, m, ArH), 5.77–5.89 (1H, m, CH), 4.85–4.95 (2H, m,
CH2@), 4.81 (1H, s, SiH), 2.13 (2H, d, J = 7.3 Hz, CH2CH@CH2); 13C
NMR (100 MHz, CDCl3): d 135.10, 134.65, 134.13, 130.25, 129.13,
115.32, 19.76; MS: m/z (%): 182 (M+, 2.07), 141 (100).
Allylchlorodimethylsilane (6d) [15c]: 1HNMR (400 MHz, CDCl3): d
5.63–5.73 (1H, m, CH), 4.74–4.82 (2H, m, CH2@), 1.74 (2H, d,
J = 7.1 Hz, CH2CH@CH2), 0.28 (6H, s, CH3Si); 13C NMR (100 MHz,
CDCl3): d 134.12, 115.78, 20.01, ꢁ2.36; MS: m/z (%): 134 (M+,
1.24), 119 (23.78), 93 (100).
2 ꢀ CH), 4.91–5.03 (4H, m, 2 ꢀ CH2@), 1.21 (12H, s, 4 ꢀ CH3); MS:
m/z (%): 278 (M+, 1.32), 263 (13.38), 201 (100); Anal. Calc. for
C16H23ClSi: C, 68.91; H, 8.31; Si, 10.07. Found: C, 68.84; H, 8.26;
Si, 10.00%.
Di-(2-methylallyl)chlorophenylsilane ( 8d): 1H NMR (400 MHz,
CDCl3): d 7.21–7.40 (5H, m, ArH), 4.75 (2H, s, 2 ꢀ CH2@), 4.64
(2H, s, 2 ꢀ CH2@), 2.15 (4H, s, 2 ꢀ Si-CH2), 1.72 (6H, s, 2 ꢀ CH3);
13C NMR (100 MHz, CDCl3): d 141.86, 135.17, 134.63, 134.10,
132.23, 130.02, 115.11, 22.38, 17.89; MS: m/z (%): 250(M+, 1.66),
235 (32.35), 195 (100); Anal. Calc. for C14H19ClSi: C, 67.03; H,
7.63; Si, 11.20. Found: C, 67.11; H, 7.56; Si, 11.15%.
Allylchloromethylbutylsilane ( 6e) [15c]: 1HNMR (400 MHz,
CDCl3): d 5.62–5.74 (1H, m, CH), 4.74–4.84 (2H, m, CH2@), 1.94–
1.35 (4H, m), 0.87–0.96 (2H, t, CH2CH3), 0.60–0.65 (3H, t, CH3CH2),
0.29 (3H, s, CH3Si); MS: m/z (%): 176 (M+, 2.32), 162 (30.28), 135
(100).
Di-((E)-but-2-enyl)chlorophenylsilane ( 8e) [15d]: 1H NMR
(400 MHz, CDCl3): d 7.28–7.55 (5H, m, ArH), 5.57–5.62 (4H, m,
2 ꢀ CH@CH), 2.16 (4H, d, J = 7.2 Hz, 2 ꢀ Si-CH2), 1.72 (6H, d,
J = 7.3 Hz, CH3); MS: m/z (%): 250(M+, 1.02), 235 (25.35), 195
(100); Anal. Calc. for C14H19ClSi: C, 67.03; H, 7.63; Si, 11.20. Found:
C, 67.09; H, 7.57; Si, 11.14%.
Chloro(2-methylbut-3-en-2-yl)methylphenylsilane ( 6f): d 7.25–
7.47 (5H, m, ArH), 5.71–5.75 (1H, m, CH), 4.91–5.03 (2H, m,
CH2@), 1.21 (6H, s,
(100 MHz, CDCl3):
2
CH3), 0.31 (3H, s, CH3Si); 13C NMR
d
138.10, 135.39, 134.77, 130.12, 127.76
3.5. General procedure for the synthesis
of allenylaralkyl silanes (10a–10k)
114.55, 24.13, 3.02; MS: m/z (%): 224 (M+, 2.03), 209 (8.23), 147
(100); Anal. Calc. for C12H17ClSi: C, 64.11; H, 7.62; Si, 12.49. Found:
C, 64.19; H, 7.70; Si, 12.55%.
Propargyl bromide (1.5 mmol) and indium (1 mmol) in dry DMF
(2 mL) were added to a three-necked flask with stirring at room
temperature under a nitrogen atmosphere. The mixture was stirred
for about 1 h. Chlorosilanes (1 mmol) were added dropwise. The
reaction mixture was stirred for 3 h and quenched with 0.1 M
hydrochloric acid (2 mL). The resulting mixture was extracted with
diethyl ether (3 ꢀ 5 mL), the diethyl ether solution was washed
with saturated NaCl (2 ꢀ 5 mL) and dried over anhydrous MgSO4.
The solvent was removed by evaporation under reduced pressure.
The crude product was purified by preparative TLC on silica gel
(cyclohexane as eluent).
Chloro(2-methylallyl)methylphenylsilane
(
6g): 1H NMR
(400 MHz, CDCl3): d 7.31–7.50 (5H, m, ArH), 4.71 (2H, s, CH2@),
2.11 (2H, s, Si-CH2), 1.70 (3H, s, CH3), 0.35 (3H, s, CH3Si); 13C
NMR (100 MHz, CDCl3): d 141.33, 135.67, 134.23, 134.01, 131.55,
129.63, 115.31, 24.23, 18.12, ꢁ2.56; MS: m/z (%): 210(M+, 1.01),
195 (13.23), 155 (100); Anal. Calc. for C11H15ClSi: C, 62.68; H,
7.17; Si, 13.32. Found: C, 62.59; H, 7.11; Si, 13.41%.
Chloro((E)-but-2-enyl)methylphenylsilane ( 6h) [15d]: 1H NMR
(400 MHz, CDCl3): d 7.28–7.55 (5H, m, ArH), 5.52–5.55 (2H, m,
CH@CH), 2.14 (2H, d, J = 7.1 Hz, Si-CH2), 1.77 (3H, d, J = 7.3 Hz,
CH3), 0.33 (3H, s, CH3Si); MS: m/z (%): 210(M+, 1.24), 195 (10.25),
155 (100).
Allenyldiphenylsilane (10a) [14a] IR: (liquid film) 3068.7, 3050.1,
2924.9, 2852.2, 2135.0, 1931.3, 1589.0, 1428.8, 1117.1 cmꢁ1 1H
;
Chloro(cyclohex-2-enyl)methylphenylsilane
(
6i): 1H NMR
NMR (400 MHz, CDCl3): d 7.25–7.58 (10H, m, ArH), 5.25 (1H, t,
J = 6.3 Hz, CH@C@CH2), 5.14 (1H, s, H-Si), 4.44 (2H, d, J = 6.3 Hz,
(400 MHz, CDCl3): d 7.26–7.46 (5H, m, ArH), 5.61–5.53 (2H, m,
CH@CH), 1.98–1.31 (7H, m, CHCH2CH2CH2), 0.29 (3H, s, CH3Si);
13C NMR (100 MHz, CDCl3): d 141.23, 135.11, 134.77, 133.56,
130.42, 129.35, 128.36, 127.88, 31.02, 26.78, 23.23, 19.13; MS:
m/z (%): 236 (M+, 7.76), 267 (19.00), 155 (100); Anal. Calc. for
C13H17ClSi: C, 65.93; H, 7.24; Si, 11.86. Found: C, 65.89; H, 7.31;
Si, 11.79%.
CH2@C@CH); 13C NMR (100 MHz, CDCl3):
d 210.88, 135.30,
133.26, 129.93, 128.04, 75.34, 68.20; MS: m/z (%): 222 (M+,
14.72), 183 (100), 144 (54.56).
Allenyltriphenylsilane (10b) [14a] IR: (liquid film) 3293.4, 3060.1,
3009.1, 1925.1, 1588.9, 1425.5, 1114.8 cmꢁ1 1H NMR (400 MHz,
;
CDCl3): d
7.23–7.64 (15H, m, ArH), 5.48 (1H, t, J = 6.2 Hz,
CH@C@CH2), 4.40 (2H, d, J = 6.2 Hz, CH2@C@CH); 13C NMR
3.4. The reaction of trichlorosilanes (RSiCl3)
with allylindium bromide (8a–8e)
(100 MHz, CDCl3): d 215.55, 135.60, 134.18, 129.98, 127.86,
76.74, 68.53; MS: m/z (%): 298 (M+, 7.22), 259 (100), 181 (17.07).
Allenyldiphenylmethylsilane (10c) [14d] IR: (liquid film) 3068.5,
3049.3, 2960.5, 2921.2, 2179.5, 1930.4, 1716.0, 1589.7, 1428.2,
Allylindium bromide (20 mmol) was prepared using the above
procedure in DM. Trichlorosilanes (10 mmol) were added drop-
wise, and then the reaction mixture was stirred for 3 h at 70 °C.
The inorganic precipitate was filtered off and washed with dry
diethyl ether. The solvent was removed by evaporation and the
residual liquid fractionally distilled.
1113.8 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.26–7.57 (10H, m,
;
ArH), 5.29 (1H, t, J = 6.3 Hz, CH@C@CH2), 4.44 (2H, d, J = 6.3 Hz,
CH2@C@CH), 0.67(3H, s, CH3); 13C NMR (100 MHz, CDCl3): d
214.47, 136.25, 134.67, 129.51, 127.89, 78.07, 68.02, ꢁ3.71; MS:
m/z (%): 236 (M+, 6.77), 221 (5.23), 197 (100), 105 (18.50).
Allenyldimethylphenylsilane ( 10d) [14a]: 1H NMR (400 MHz,
CDCl3): d7.46–7.68 (5H, m, ArH), 5.19 (1H, t, J = 6.2 Hz, CH@C@CH2),
4.53 (2H, d, J = 6.1 Hz, CH2@C@CH), 0.53(6H, s, CH3); 13C NMR
Diallylchlorophenylsilane (8a) [9] IR: mmax (liquid film) 3073.0,
3002.4, 2974.2, 2919.8, 1632.0, 1428.9, 1121.7 cmꢁ1 1H NMR
;
(400 MHz, CDCl3): d 7.33–7.47 (5H, m, ArH), 5.74–5.82 (2H, m,
2 ꢀ CH), 4.98–5.02 (4H, t, 2 ꢀ CH2@), 2.09–2.11 (4H, d, J = 7.3 Hz,
2 ꢀ CH2CH@CH2); 13C NMR (100 MHz, CDCl3): d 133.85, 131.38,
130.62, 128.09, 127.77, 116.34, 15.32; MS: m/z (%): 222 (M+,
7.63), 183 (35.03), 181 (100), 145 (84,91), 142 (4.27).
(100 MHz, CDCl3):
d 212.38, 139.87, 133.67, 133.06, 129.31,
127.87, 79.48, 67.44, ꢁ2.38; MS: m/z (%): 174 (M+, 18.62), 159
(14.45), 135 (100), 105 (13.01).
Allenyldimethylvinylsilane ( 10e) [14e]: 1H NMR (400 MHz,
CDCl3): d 5.72–5.85 (3H, m, CH2@CH), 5.16 (1H, t, J = 6.2 Hz,
CH@C@CH2), 4.48 (2H, d, J = 6.2 Hz, CH2@C@CH), 0.60 (6H, s,
CH3); 13C NMR (100 MHz, CDCl3): d 212.33, 142.13, 139.56,
75.28, 66.15, ꢁ2.76; MS: m/z (%): 126 (M+, 12.80), 83 (25.94), 73
(100).
Diallylchloromethylsilane (8b) [9]: 1H NMR (400 MHz, CDCl3): d
5.70–5.82 (2H, m, 2 ꢀ CH), 4.95–5.04 (4H, m, 2 ꢀ CH2@), 2.10 (4H,
d, J = 7.1 Hz, 2 ꢀ CH2CH@CH2), 0.30 (3H, s, CH3Si); 13C NMR
(100 MHz, CDCl3): d 133.87, 114.23, ꢁ3.36; MS: m/z (%): 160 (M+,
0.35), 109 (100).
Di-(2-methylbut-3-en-2-yl)chlorophenylsilane ( 8c): 1H NMR
(400 MHz, CDCl3): d 7.28–7.47 (5H, m, ArH), 5.74–5.80 (2H, m,
Allenyltrimethylsilane (10f) [14a]: 1H NMR (400 MHz, CDCl3): d
5.29 (1H, t, J = 6.2 Hz, CH@C@CH2), 4.42 (2H, d, J = 6.2 Hz,

3778
Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
CH2@C@CH), 0.63 (9H, s, CH3); 13C NMR (100 MHz, CDCl3): d
211.18, 77.32, 67.72, ꢁ3.13; MS: m/z (%): 112 (M+, 9.23), 73 (100).
(3-Methylallenyl)diphenylsilane (10g) [14d]: 1H NMR (400 MHz,
CDCl3): d 7.26–7.65 (10H, m, ArH), 5.16 (1H, s, H-Si), 4.43 (2H, s,
CH2@C@C), 1.84 (3H, s, CH3); 13C NMR (100 MHz, CDCl3): d
211.88, 135.56, 132.95, 129.91, 128.02, 84.73, 68.72, 16.57; MS:
m/z (%): 236 (M+, 10.65), 221 (16.32), 183 (100), 158 (16.89).
(3-Methylallenyl)triphenylsilane (10h) [14e]: 1H NMR (400 MHz,
CDCl3): d7.21–7.65 (15H, m, ArH), 4.41 (2H, s, CH2@C@C), 1.84 (3H,
s, CH3); 13C NMR (100 MHz, CDCl3): d212.57, 135.13, 133.56,
129.87, 128.13, 85.12, 69.54, 17.11; MS: m/z (%): 312 (M+, 9.35),
297 (13.68), 259 (100), 235 (21.35).
d 211.37, 76.76, 67.13, ꢁ3.78; MS: m/z (%): 135 (M+, 15.96), 121
(62.41), 97 (100).
Diallenylmethylbutylsilane (11e) [14d] IR: (liquid film) 2924.6,
2854.8, 1461.0, 1377.1, 1257.7, 1021.6, 908.3, 735.5 cmꢁ1 1H
;
NMR (400 MHz, CDCl3): d 5.31 (2H, t, J = 6.2 Hz, 2 ꢀ CH@C@CH2),
4.42 (4H, d, J = 6.2 Hz, 2 ꢀ CH2@C@CH), 1.17–1.71 (9H, m, C4H9),
0.75 (3H, s, CH3Si); 13C NMR (100 MHz, CDCl3): d 212.56, 77.31,
76.68, 33.50, 29.69, 24.83, 14.58; MS: m/z (%): 184 (M+, 13.23),
169 (45.61), 145 (100).
Di-(3-methylallenyl)methylphenylsilane ( 11f) [14e]: 1H NMR
(400 MHz, CDCl3):
d 7.26–7.60 (5H, m, ArH), 4.36 (4H, d,
J = 6.4 Hz, 2 ꢀ CH2@C), 1.78 (6H, s, 2 ꢀ CH3-C(Si)@), 0.46 (3H, s,
CH3-Si); 13C NMR (100 MHz, CDCl3): d 211.34, 135.61, 135.13,
129.73, 128.12, 85.13, 68.78, 16.54, ꢁ3.68; MS: m/z (%): 226 (M+,
1.21), 211 (62.41), 97 (100).
(3-Methylallenyl)diphenylmethylsilane ( 10i) [14d] IR: (liquid
film) 3068.5, 3049.3, 2917.4, 2856.0, 1931.0, 1589.3, 1428.2,
1113.0 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.26–7.68 (10H, m,
;
ArH), 4.40 (2H, s, CH2@C@C), 1.78 (3H, s, CH3-C@), 0.62 (3H, s,
CH3-Si); 13C NMR (100 MHz, CDCl3): d 211.18, 135.59, 135.03,
129.55, 127.83, 86.78, 68.53, 16.37, ꢁ3.86; MS: m/z (%): 250 (M+,
8.22), 197 (100), 105 (14.21).
Di-(buta-1,2-dienyl)methylphenylsilane ( 11g) [14e]: 1H NMR
(400 MHz, CDCl3): d 7.26–7.63 (5H, m, ArH), 4.82–4.86 (2H, m,
2 ꢀ CH(CH3)@C), 4.43 (2H, s, 2 ꢀ CHSi@C), 1.75 (6H, d, J = 6.8 Hz,
2 ꢀ CH3-CH@), 0.46 (3H, s, CH3-Si); 13C NMR (100 MHz, CDCl3): d
210.56, 135.63, 135.23, 129.77, 128.34, 86.34, 69.13, 15.88,
ꢁ3.91; MS: m/z (%): 226 (M+, 2.13), 211 (22.23), 145 (100).
(3-Methylallenyl)trimethylsilane (10j) [14d]: 1H NMR (400 MHz,
CDCl3): d 4.41 (2H, s, CH2@C@C), 1.76 (3H, s, CH3-C@), 0.55 (9H,
s, CH3-Si); 13C NMR (100 MHz, CDCl3): d 210.72, 90.03, 69.12,
17.10, ꢁ3.81; MS: m/z (%): 126 (M+, 12.80), 83 (25.94), 73 (100).
Buta-1, 2-dienyldiphenylsilane (10k) [14e]: 1H NMR (400 MHz,
CDCl3): d 7.21–7.61 (10H, m, ArH), 5.13 (1H, s, H-Si), 4.82–4.85
(1H, m, CH(CH3)@C), 4.42 (1H, s, CHSi@C), 1.78 (3H, d, J = 6.8 Hz,
CH3-CH@); 13C NMR (100 MHz, CDCl3): d 211.93, 135.71, 133.34,
129.95, 128.63, 85.65, 69.12, 15.36, ꢁ3.77; MS: m/z (%): 236 (M+,
12.32), 221 (17.11), 183 (100), 158 (21.33).
3.7. General procedure for the synthesis of allenyl substituted
chlorosilanes (12a–12g)
Allylindium bromide (10 mmol) was prepared using the above
procedure in DMI. Dichlorosilanes (10 mmol) were added drop-
wise. The reaction mixture was stirred for about 3 h at room tem-
perature. The inorganic precipitate was filtered off and washed
with dry diethyl ether. The solvent was removed by evaporation
and the residual liquid fractionally distilled.
3.6. General procedure for the synthesis of diallenyl
Allenylchloromethylphenylsilane ( 12a): 1H NMR (400 MHz,
substituted silanes (11a–11g)
CDCl3): d 7.18–7.56 (5H, m, ArH), 5.09 (1H, t, J = 6.2 Hz,
CH@C@CH2), 4.40 (2H, d, J = 6.2 Hz, CH2@C@CH), 0.42(3H, s, CH3-
Si); 13C NMR (100 MHz, CDCl3): d 214.32, 135.82, 134.38, 128.77,
127.82, 76.96, 70.10, ꢁ3.34; MS: m/z (%): 194 (M+, 5.12), 155
(100), 140 (72.57); Anal. Calc. for C10H11ClSi: C, 61.68; H, 5.69; Si,
14.42. Found: C, 61.59; H, 5.62; Si, 14.49%.
Propargylindium bromide (2 mmol) was prepared using the
above procedure. Dichlorosilanes (1 mmol) were added dropwise.
The reaction mixture was stirred for3 h and then quenched with
0.1 M hydrochloric acid (2 mL). The resulting mixture was ex-
tracted with diethyl ether (3 ꢀ 5 mL), the diethyl ether solution
was washed with saturated NaCl (2 ꢀ 5 mL) and dried over anhy-
drous MgSO4. The solvent was removed by evaporation under re-
duced pressure. The crude product was purified by preparative
TLC on silica gel (cyclohexane as eluent).
Allenylchlorodiphenylsilane ( 12b) [14c]: 1H NMR (400 MHz,
CDCl3):
CH@C@CH2 ),
d
7.24–7.55 (10H, m, ArH), 5.27 (1H, t, J = 6.2 Hz,
CH2@C@CH); 13C NMR (100 MHz,
4.44 (2H, d, J = 6.2 Hz,
CDCl3): d 213.53, 135.34, 134.25, 129.91, 128.10, 87.52, 69.78;
MS: m/z (%): 256 (M+, 8.22), 219 (72.35), 105 (100).
Diallenylmethylphenylsilane (11a) [14a] IR: (liquid film) 3069.2,
2961.0, 2924.8, 2856.2, 2180.1, 1931.0, 1721.4, 1620.6, 1428.0,
Allenylchlorophenylsilane ( 12c): 1H NMR (400 MHz, CDCl3): d
7.20–7.59 (5H, m, ArH), 5.30 (1H, t, J = 6.3 Hz, CH@C@CH2), 5.17
(1H, s, H-Si), 4.40 (2H, d, J = 6.3 Hz, CH2@C@CH); 13C NMR
(100 MHz, CDCl3): d 212.01, 136.23 134.76, 131.36, 129.89, 75.88,
68.32; MS: m/z (%): 180 (M+, 6.12), 165 (35.68), 141 (100); Anal.
Calc. for C9H9ClSi: C, 59.82; H, 5.02; Si, 15.54. Found: C, 59.77; H,
5.08; Si, 15.61%.
1258.3 cmꢁ1 1H NMR (400 MHz, CDCl3): d 7.23–7.64 (5H, m,
;
ArH), 5.11 (2H, t, J = 6.2 Hz, 2 ꢀ CH@C@CH2), 4.42 (4H, d,
J = 6.2 Hz, 2 ꢀ CH2@C@CH), 0.46 (3H, s, CH3-Si); 13C NMR
(100 MHz, CDCl3):
d 214.16, 136.42, 134.08, 129.76, 128.06,
77.96, 68.09, ꢁ3.91; MS: m/z (%): 198 (M+, 6.86), 159 (100), 131
(72.57).
Allenylchlorodimethylsilane ( 12d) [14d]: 1H NMR (400 MHz,
Diallenydiphenylsilane ( 11b) [14a] IR: (liquid film) 3069.4,
3049.6, 2917.7, 2856.2, 2181.4, 1928.9, 1720.4, 1667.4, 1589.4,
CDCl3): d 5.29 (1H, t, J = 6.3 Hz, CH@C@CH2), 4.44 (2H, d,
J = 6.3 Hz, CH2@C@CH), 0.67(6H, s, CH3); 13C NMR (100 MHz,
CDCl3): d 211.13, 76.35, 67.01, ꢁ4.56; MS: m/z (%): 132 (M+,
6.23), 83 (100), 48 (53.12).
1429.2, 1116.2 cmꢁ1
;
1H NMR (400 MHz, CDCl3): d 7.23–7.58
(10H, m, ArH), 5.31 (2H, t, J = 6.3 Hz, 2 ꢀ CH@C@CH2), 4.42 (4H,
d, J = 6.3 Hz, 2 ꢀ CH2@C@CH); 13C NMR (100 MHz, CDCl3):
d
Allenylchloromethylbutylsilane (12e): 1H NMR (400 MHz, CDCl3):
d 5.33 (1H, t, J = 6.2 Hz, CH@C@CH2), 4.38 (2H, d, J = 6.2 Hz,
CH2@C@CH), 1.13–1.80 (9H, m, C4H9), 0.58 (3H, s, CH3Si); 13C
NMR (100 MHz, CDCl3): d 211.89, 77.42, 76.14, 33.35, 30.12,
25.13, 14.67; MS: m/z (%): 174 (M+, 9.35), 159 (39.46), 135 (100);
Anal. Calc. for C8H15ClSi: C, 54.99; H, 8.65; Si, 16.07. Found: C,
54.91; H, 8.61; Si, 16.01%.
210.28, 135.12, 134.21, 129.83, 128.10, 87.47, 69.89; MS: m/z
(%): 260 (M+, 13.36), 221 (84.91), 182 (30.31), 105 (100).
Diallenylphenylsilane (11c) [14d]: 1H NMR (400 MHz, CDCl3): d
7.21–7.53 (5H, m, ArH), 5.29 (2H, t, J = 6.2 Hz, 2 ꢀ CH@C@CH2),
5.14 (1H, s, H-Si), 4.43 (4H, d, J = 6.3 Hz, 2 ꢀ CH2@C@CH); 13C
NMR (100 MHz, CDCl3): d 211.13, 135.82, 134.13, 130.13, 129.13,
75.67, 68.78; MS: m/z (%): 184 (M+, 9.12), 145 (76.12), 106 (100).
Diallenyldimethylsilane (11d) [14d]: 1H NMR (400 MHz, CDCl3):
d 5.33 (2H, t, J = 6.2 Hz, 2 ꢀ CH@C@CH2), 4.44 (4H, d, J = 6.2 Hz,
2 ꢀ CH2@C@CH), 0.62 (6H, s, CH3Si); 13C NMR (100 MHz, CDCl3):
(3-Methylallenyl)chloromethylphenylsilane (12f) [14e]: 1H NMR
(400 MHz, CDCl3):
CH2@C@C), 1.77 (3H, s, CH3-C@), 0.62 (3H, s, CH3-Si); 13C NMR
(100 MHz, CDCl3): 211.36, 135.76, 135.35, 129.88, 127.13,
d 7.26–7.68 (5H, m, ArH), 4.40 (2H, s,
d

Z. Li et al. / Journal of Organometallic Chemistry 693 (2008) 3771–3779
3779
86.25, 68.48, 16.02, ꢁ4.23; MS: m/z (%):208 (M+, 8.33), 193 (41.23),
155 (100).
(e) H. Sasabe, N. Kihara, K. Mizuno, A. Ogawa, T. Takata, Tetrahedron Lett. 46
(2005) 3851;
(f) S.V. Maifeld, M.N. Tran, D. Lee, Tetrahedron Lett. 46 (2005) 105;
(g) Y. Otomaru, T. Hayashi, Tetrahedron: Asymmetr. 15 (2004) 2647.
[7] (a) For reviews see: B. Marciniec, C. Pietraszuk, Curr. Org. Chem. 7 (2003)
691;
Buta-1,2-dienylchloromethylphenylsilane ( 12g) [14e]: 1H NMR
(400 MHz, CDCl3): d 7.26–7.65 (5H, m, ArH), 4.88–4.93 (1H, m,
CH(CH3)@C), 4.46 (1H, d, J = 6.2 Hz, SiCH@C), 1.56 (3H, d,
J = 6.8 Hz, CH3-C@), 0.42(3H, s, CH3-Si); 13C NMR (100 MHz, CDCl3):
d 211.71, 135.13, 133.76, 130.03, 128.78, 85.52, 68.87, 15.77,
ꢁ4.13; MS: m/z (%): 208 (M+, 7.12), 193 (33.15), 155 (100).
(b) B. Marciniec, C. Pietraszuk, in: R.H. Grubbs (Ed.), Handbook of Metathesis,
Wiley/VCH, 2003 (Chapter 2.13);
(c) B. Marciniec, in: B. Cornils, W.A. Hermann (Eds.), Applied Homogeneous
Catalysis with Organometallic Compounds, VCH, Weinheim, 2002 (Chapter
2.6);
(d) J.A. Reichl, D.H. Berry, Adv. Organomet. Chem. 43 (1998) 203;
(e) B. Marciniec, Appl. Organomet. Chem. 14 (2000) 527.
[8] (a) M. Jankowska, O. Shuvalova, N. Bespalova, M. Majchrzak, B. Marciniec, J.
Organomet. Chem. 690 (2005) 4492;
Acknowledgements
We are grateful to the Natural Science Foundation of Zhejiang
Province (Project No. Y404380) and Qianjiang Personal Program
(2008R10018) for financial support.
(b) B. Marciniec, D. Chadyniak, S. Krompiec, J. Mol. Cat. A: Chem. 224 (2004)
111;
(c) M. Jankowska, B. Marciniec, C. Pietraszuk, J. Cytarska, M. Zaidlewicz,
Tetrahedron Lett. 45 (2004) 6615;
(d) B. Marciniec, D. Chadyniak, S. Krompiec, Tetrahedron Lett. 45 (2004)
4065.
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