Controlled introduction of allylic group to chlorosilanes

Article abstract of DOI:10.1016/j.jorganchem.2006.07.023

Allylation of chlorosilanes has been achieved with allylsamarium bromide, especially in a controlled manner. Thus allylation of trisubstituted chlorosilanes (R₃SiCl) afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. Dichlorosilanes (R₂SiCl₂) can either afford monoallylated silanes or diallylated silanes depending on the amount of allylsamarium bromide used. Similarly, trichlorosilanes (RSiCl₃) can selectively afford mono-, di-, and tri-allylation products. Finally, perchlorosilane (SiCl₄) was allylated stepwise and the corresponding silanes containing one, two, three or four allylic groups, respectively, were obtained in satisfactory yields.

Full text of DOI:10.1016/j.jorganchem.2006.07.023

Journal of Organometallic Chemistry 691 (2006) 4740–4746
www.elsevier.com/locate/jorganchem
Controlled introduction of allylic group to chlorosilanes
*
*
Zhifang Li, Xiaojun Cao, Guoqiao Lai , Jinhua Liu, Yong Ni, Jirong Wu, Huayu Qiu
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Educations, Hangzhou Teachers College, Wenyi Road 222,
Hangzhou 310012, PR China
Received 10 June 2006; received in revised form 13 July 2006; accepted 18 July 2006
Available online 1 August 2006
Abstract
Allylation of chlorosilanes has been achieved with allylsamarium bromide, especially in a controlled manner. Thus allylation of tri-
substituted chlorosilanes (R3SiCl) afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. Dichlorosilanes (R2SiCl2) can
either afford monoallylated silanes or diallylated silanes depending on the amount of allylsamarium bromide used. Similarly, trichloro-
silanes (RSiCl3) can selectively afford mono-, di-, and tri-allylation products. Finally, perchlorosilane (SiCl4) was allylated stepwise and
the corresponding silanes containing one, two, three or four allylic groups, respectively, were obtained in satisfactory yields.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Controlled allylation; Allyl samarium bromide; Alkenyl groups; Chlorosilanes
1. Introduction
anes was also described. These methods are useful for the
preparation of novel and well-known silicon-containing
alkenes, but it did not work well for synthesis of unsatu-
rated chlorosilanes [5,6]. Our recent work in the prepara-
tion of polysilanes as functional materials requires
unsaturated chlorosilanes (those containing chloro group
are most desirable) as monomers. In view of this, we devel-
oped a mild, safe, and more efficient method for the con-
trolled introduction of allylic group to several kinds of
chlorosilanes.
We previously found that allylsamarium bromide is a
versatile reagent for the introduction of allylic group to a
variety of substrates such as formanilides, lactones and lac-
tams [7]. Herein we describe the results of our study on the
allylation of chlorosilanes with allylsamarium bromide.
Substituted allyl or vinylsilanes have become a com-
monly used class of organosilicon reagents in organic syn-
thesis. Hydrolysis and dehydration of these products
yielded polysiloxanes which retained the unsaturated
groups, permitting additional polymerization across the
double bonds to synthesize the functional polymers [1].
The reactions of Grignard reagents with chlorosilanes
and alkoxysilanes offer a convenient route to the synthesis
of various industrial useful organosilicon compounds.
However, only moderate yields of the products could be
obtained in the preparation of unsaturated chlorosilanes
with this method [2]. Recently, some modified approaches
have been reported for the synthesis of unsaturated
organosilicon compounds, such as hydrosilylation and
silylmetallation and/or carbosilylation of alkynes or hydro-
metallation and hydrogenation of alkynylsilanes [3,4].
More recently, ruthenium catalyzed synthesis of vinylsil-
2. Results and discussion
2.1. The reaction of trisubstituted chlorosilanes (R3SiCl)
with allylsamarium bromide
Currently the most practical method for the synthesis of
trisubstituted allylsilanes is a Grignard type reaction of
chlorosilanes with allylmagnesium chloride, but other
*
Corresponding authors. Tel.: +86 571 28868081; fax: +86 571
28865135.
E-mail address: gqlai@hztc.edu.cn (G. Lai).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.07.023

Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
4741
approaches could provide important advantages [8]. For
example, the use of more reactive organolithium reagents
rather than Grignard reagents, affords the trialkylsilane
with bulky substituents [9]; the electrolysis of appropriate
chlorosilanes gives the symmetrical difunctional disilanes
in good yield [10]; palladium with SmI2–HMPA system cat-
alyzed stereoselective synthesis of allylsilanes [11]. We
found that when trisubstituted chlorosilanes (R3SiCl) were
treated with allylsamarium bromide in THF at room tem-
perature, allyl substituted organosilicons were obtained in
good yields (Scheme 1). The chlorosilanes and allylsamar-
ium bromide were used in a ratio of 1:1.1.
the corresponding products in high yield (Table 1, entries
2–5). The product formation was ascertained by TLC mon-
itoring and the product isolation was achieved by quench-
ing the reaction with dilute hydrochloric acid followed by
extraction. The aliphatic chlorosilanes such as chlorotri-
methylsilane also react with allylsamarium bromide
smoothly and the corresponding allyltrimethylsilane was
obtained in good yield albeit lower temperature (À10 ꢁC)
was required (entry 6).
2.2. The reaction of dichlorosilanes (R2SiCl2) with
allylsamarium bromide
The reactions of arylsubstituted chlorosilanes with all-
ylsamarium bromide were completed within 2 h to give
Aryl- and aralkyl-unsaturated chlorosilanes, in which
the aryl and aralkyl groups are directly linked with silicon,
were widely used in the preparation of functional polysilox-
anes with good thermal stability and a rapid cure [12]. It
was, therefore, of interest to prepare these silicon deriva-
tives in order to obtain compounds which when mixed with
methyl or phenyl polysiloxanes would reduce the cure time
of these conventional silicon resins as well as improve cer-
tain physical properties of these polymers. These unsatu-
rated chlorosilanes were first reported by Hurd [13]. Pure
aryl or aralkyl allyldichlorosilanes were prepared from
allyl- and vinyltrichlorosilane and the appropriate Grig-
nard compound [14]. However, in most reactions carried
Br
+
THF, r.t.
I2 (Cat.)
SmBr
+
Sm
SiR3
THF, r.t.
SmBr
R3SiCl
1
2
3
R3 = H, Aryl, Alkyl, Vinyl
Scheme 1.
Table 1
The reaction of trisubstituted chlorosilanes (R3SiCl) with allylsamarium bromidea
Entry
1c
Substrate
Ph3SiCl
Time (h)
2.5
Product
Yieldsb (%)
97
3a
Ph3Si
2
3
4
Ph2MeSiCl
PhMe2SiCl
Ph2HSiCl
1.5
1.5
1.5
98
99
96
3b
Ph2MeSi
PhMe2Si
Ph2HSi
3c
3d
5
AllylMePhSiCl
Me3SiCl
2
88
78
3e
AllylMePhSi
Me3Si
6d
2.5
3f
7
Me3SiCl
2.5
0e
3f
Me3Si
a
Unless otherwise noted, chlorosilanes (1 mmol) were allowed to react with Sm (1.1 mmol) and allyl bromide (1 mmol) in THF at room temperature for
1.5–2.5 h.
b
Isolated yields based on 1.
At 65 ꢁC.
c
d
e
At À10 ꢁC.
Complex mixture.

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Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
Table 2
out between Grignard reagent and chlorosilanes to form
partially substituted arylchlorosilanes, successive substitu-
tion products were always formed [15]. In our studies for
the construction of Si–C bond, we found that the substitu-
tion reaction between dichlorosilanes (R1R2SiCl2) and all-
ylsamarium bromide could be controlled at the desired
mono- or di- substituted manner. When dichlorosilanes
(R1R2SiCl2) and allylsamarium bromide were used in a
ratio of 1:1, the monoallyl substituted organosilicons (5)
were obtained in excellent yields; while the 1:2 ratio gave
the substituted allylsilanes (6) (Scheme 2) almost quantita-
tively. It should be noted that the monoallylation of
dichlorosilanes (R2SiCl2) were generally clean and no
gem-diallylated products could be detected in the 1H
NMR spectra of the crude products.
The reaction of dichlorosilanes (R2SiCl2) with allylsamarium bromidea
Entry
1
Substrate
Time (h)
1
Product
Yieldsb (%)
PhMeSiCl2
97
Me
Si
Ph
6a
1
1
95
99
Me
Si
Ph
Cl
5a
2
Ph2SiCl2
Ph
Si
Ph
6b
On the basis of the good results obtained with simple
dichlorosilanes, it seemed logical to investigate the possibil-
ity of extending this methodology to carry out controlled
allylation of dichloromethylvinylsilane with an attempt to
obtain allylchloromethylvinylsilane or diallylmethylvinylsi-
lane (entry 3). The results and the scope of this reaction are
summarized in Table 2, which clearly indicates that the
present strategy may afford a general allylation protocol
for the synthesis of allylsubstituted chlorosilanes.
1
4
98
90
Ph
Si
Ph
Cl
5b
Me
Si
6c
3c
VinylMeSiCl2
4
86
Me
Si
2.3. The reaction of trichlorosilanes (RSiCl3) with
allylsamarium bromide
Cl
5c
a
Unless otherwise specified, chlorosilanes (1 mmol) were allowed to
react with allylsamariumbromide (1–2 mmol) in THF at room tempera-
ture for 1–2 h.
With the success for the synthesis of allyl substituted
organosilanes and chlorosilanes, we subsequently investi-
gated the allylation of trichlorosilanes (RSiCl3) with
allylsamarium bromide. When trichlorophenylsilane (1
mmol) was treated with allylsamarium bromide (3 mmol),
the triallylphenylsilane (7) was obtained in excellent yield
(99%), where a high chemical selectivity was observed with
mono- or diallyl substituted silane contamination. When tri-
chlorophenylsilane and allylsamarium bromide were used in
a ratio of 1:2 or 1:1, the diallylchlorophenylsilane (8) and
allyldichlorophenylsilane (9) were obtained, respectively
(Scheme 3). Under the similar reaction conditions, trichloro-
methylsilane also reacted with allylsamarium bromide
b
Isolated yields based on 4.
At À10 to 0 ꢁC.
c
smoothly, giving the corresponding products in good yields.
The results are summarized in Table 3.
2.4. The reaction of perchlorosilane (SiCl4) with
allylsamarium bromide
Scott and Frisch reported that the reaction of allyl Grig-
nard reagent with SiCl4 led to a mixture of allyltrichloros-
ilane
(30.5%),
diallyldichlorosilane
(35.5%)
and
triallylchlorosilane (25.5%) [13]. Our study here found that
the reaction of SiCl4 at room temperature could afford any
of them (10, 11, 12 or13) as the main product depending
upon the amounts of the allylsamarium bromide added,
thus having preparative value (Scheme 4).
In conclusion, we present the novel selective allylation of
chlorosilanes with allylsamarium bromide. By applying this
method, aryl and aralkyl unsaturated chlorosilanes as well
as diallyl chlorosilanes containing different allyl groups
were prepared conveniently. The new types of allylsubsti-
tuted chlorosilanes prepared herein possess unsaturated
carbon–carbon bonds and will meet our further require-
ments to permit additional polymerization across the dou-
ble bonds so as to synthesize functional polymers.
SmBr
R1
Si
R2
(1 mmol)
2
Cl
5
6
THF, r.t.
R1R2SiCl2
SmBr
4 (1 mmol)
R1
( 2 mmol)
2
Si
R2
R1, R2 = H, Aryl, Alkyl, Vinyl
Scheme 2.

Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
4743
SmBr
(3 mmol)
SmBr
Si
R
Si
(40 mmol)
7
10 (98%)
SmBr
R
SmBr
(2 mmol)
THF
Si
RSiCl3
(30 mmol)
Si
Cl
Cl
(1 mmol)
8
9
11 (81%)
THF
r.t.
SiCl4
SmBr
Cl
SmBr
Cl
(1 mmol)
R = Me, Ph
(10 mmol)
R Si
Cl
(20 mmol)
Si
Cl
12 (75%)
13 (71%)
SmBr
Scheme 3.
Cl
(10 mmol)
Cl Si
Cl
Table 3
The reaction of trichlorosilanes (RSiCl3) with allylsamarium bromidea
Scheme 4.
Entry
1
Substrate
PhSiCl3
Time (h)
1
Product
Yieldsb (%)
97
Si
was performed on a VARIO EL-3 instrument. Metallic
samarium, the starting material chlorosilanes and all sol-
vents were purchased from commercial sources and were
used without further purification. Allylsamarium bromide
was sensitive to air and water, must be stored in a sealed
vessel under nitrogen.
Ph
7a
8a
1
95
Ph
Si
Cl
0.5
1.5
99
97
Ph
Si
3.1. General procedure for the synthesis of allylaralkyl
silanes (3a–e)
Cl
Cl
9a
2
MeSiCl3
Allyl bromide (4 mmol) and samarium (2.2 mmol) with a
catalytic amount of iodine (0.01 mmol) in dry THF (10 mL)
were added to a three-necked flask with stirring at room
temperature under a nitrogen atmosphere. The mixture
was stirred for about 5 min, and a purple color was formed.
Chlorosilanes (2 mmol) were added dropwise, the purple
color of the mixture disappeared gradually. The reaction
mixture was stirred for 1–2 h and then was quenched with
0.1 M hydrochloric acid (10 mL). The resulting mixture
was extracted with diethyl ether (3 · 15 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–ethyl acetate (8:1) as eluent).
Si
Me
7b
8b
1.5
1.5
95
99
Me
Si
Cl
Me
Si
Cl
Cl
9b
a
Chlorosilanes (1 mmol) were allowed to react with allylsamarium
bromide for 1–2 h, the respective amounts depending upon the desired
allylic silanes.
b
Isolated yields based on RSiCl3 used.
3. Experimental
3.1.1. Allyltriphenylsilane (3a)
Tetrahydrofuran was distilled from sodium-benzophe-
none immediately prior to use. All reactions were con-
ducted under a nitrogen atmosphere. Melting points are
IR: mmax (KBr) 3066.0, 3041.0, 2996.0, 2923.3, 2863.4,
1628.1, 1427.3, 1112.6 cmÀ1; 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, q, CH2@), 2.38–2.40 (2H, d, 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). Anal.
Calc. C21H20Si: C, 83.94; H, 6.71; Si, 9.35. Found: C,
83.89; H, 6.76; Si, 9.38%.
1
uncorrected. H NMR spectra were recorded on a BRU-
KER 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
hertz. IR spectra were taken as thin films with a BRUKER
TENSOR-27 infrared spectrometer. Elemental analysis

4744
Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
3.1.2. Allyldiphenylmethylsilane (3b)
IR: mmax (liquid film) 3069.6, 2924.0, 2853.5, 1630.4,
diethyl ether (3 · 20 mL), the diethyl ether solution was
washed with saturated NaCl (2 · 20 mL) and dried over
anhydrous MgSO4. The solvent was removed by evapora-
tion under reduced pressure. The residual liquid was frac-
tionally distilled.
1
1427.6, 1251.5, 1151.9, 1112.9 cmÀ1; H NMR (400 MHz,
CDCl3): d 7.32–7.36 (10H, m, ArH), 5.74–5.85 (1H, m,
CH), 4.85–4.93 (2H, t, CH2@), 2.06–2.08 (2H, d,
CH2CH@CH2), 0.55 (3H, s, CH3); 13C NMR (100 MHz,
CDCl3): d 136.41, 134.41, 133.92, 129.16, 127.70, 114.13,
22.03, À4.95; MS: m/z (%): 278 (M+, 4.00), 198 (27.09),
197 (100). Anal. Calc. C16H18Si: C, 80.61; H, 7.61; Si,
11.78. Found: C, 80.56; H, 7.57; Si, 11.86%.
3.2.1. Allyltrimethylsilane (3f)
1H NMR (400 MHz,CDCl3): d 5.66–5.71 (1H, m, CH),
4.77–4.83 (2H, m, CH2@), 1.73–1.75 (2H, d,
CH2CH@CH2), 0.21–0.33 (9H, s, CH3); MS: m/z (%):
114 (M+, 2.56), 74 (29.04), 73(43.76), 9 (46.08), 45(100).
Anal. Calc. C6H14Si: C, 63.07; H, 12.35; Si, 24.58. Found:
C, 62.89; H, 12.22; Si, 24.46%.
3.1.3. Allyldimethylphenylsilane (3c)
IR: mmax (liquid film) 3070.3, 2998.6, 2957.6, 2915.9,
1630.0, 1426.8, 1249.9, 1155.4, 1114.3 cmÀ1 1H NMR
;
(400 MHz, CDCl3): d 7.33–7.50 (5H, m, ArH), 5.72–5.80
(1H, m, CH), 4.83–4.88 (2H, t, CH2@), 1.74–1.76 (2H, d,
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, À3.70; MS: m/z (%): 176 (M+, 1.00), 161 (0.88), 136
(12.52), 135 (100), 105 (2.97). Anal. Calc. C11H16Si: C,
74.93;H, 9.19;Si, 15.93. Found:C, 74.86; H, 9.11; Si, 15.89%.
3.3. General procedure for the synthesis of allyl substituted
chlorosilanes (5a–c)
Allylsamarium bromide (20.2 mmol) was prepared using
the above procedure. Dichlorosilanes (20 mmol) were
added dropwise, the purple color of the mixture disap-
peared slowly. The reaction mixture was stirred for 1–2 h.
The inorganic precipitate was filtered off and washed
repeatedly with dry ether. The filtrate was then freed from
any solvent and the residual liquid fractionally distilled.
3.1.4. Allyldiphenylsilane (3d)
IR: mmax (liquid film) 3069.3, 3003.1, 2972.5, 2920.0,
2125.3, 1629.8, 1427.0, 1155.0, 1114.1 cmÀ1 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, 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). Anal. Calc. C15H16Si: C, 80.30; H,
7.19; Si, 12.52. Found: C, 80.25; H, 7.12; Si, 12.46%.
3.3.1. Allylchloromethylphenylsilane (5a)
IR: mmax (liquid film) 3071.2, 2969.5, 1630.5, 1427.8,
1256.2, 1157.0, 1118.3 cmÀ1; 1H 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, 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, À1.62; MS:
m/z (%): 161 (100), 155 (21.83), 121 (37.22), 105 (14.01).
3.1.5. Diallylmethylphenylsilane (3e)
IR: mmax (liquid film) 3072.5, 2971.3, 2916.2, 1630.0,
3.3.2. Allylchlorodiphenylsilane (5b)
1
1426.9, 1252.1, 1154.2, 1113.2 cmÀ1; H NMR (400 MHz,
IR: mmax (liquid film) 3069.9, 3023.2, 2919.9, 1630.0,
1590.6, 1428.0, 1117.5 cmÀ1; 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, m, CH2CH@CH2);
13C NMR (100 MHz, CDCl3): d 133.79, 130.27, 130.05,
129.32, 127.56, 114.60, 19.83; MS: m/z (%): 258 (M+,
2.54), 217 (100), 181 (13.60).
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,
2 · CH2CH@CH2), 0.28 (3H, s, CH3); 13C NMR
(100 MHz, CDCl3): d 136.71, 134.05, 133.79, 129.06,
127.62, 113.73, 21.44, À5.98; MS: m/z (%): 202 (M+, 4.1),
161 (100), 121 (30.5), 105 (11.9).
3.2. General procedure for the synthesis of
allyltrimethylsilane (3f)
3.4. General procedure for the synthesis of diallyl substituted
silanes (6a–c)
Allyl bromide (20.1 mmol) and samarium (20 mmol)
with a catalytic amount of iodine (0.1 mmol) in dry THF
(20 mL) were added to a three-necked flask with stirring
at room temperature under a nitrogen atmosphere. The
mixture was stirred for about 5 min, and a purple color
was formed. Then the mixture was stirred for additional
1.5 h. Chlorotrimethylsilane (20 mmol) in THF (5 mL)
were added dropwise at À10 ꢁC, and the purple color of
the mixture faded gradually. The reaction mixture was stir-
red for 2.5 h and then was quenched with 0.1 M hydrochlo-
ric acid (20 mL). The resulting mixture was extracted with
Allylsamarium bromide was prepared using the above
procedure. Dichlorosilanes (2 mmol) were added dropwise,
the purple color of the mixture disappeared slowly. The
reaction mixture was stirred for 1–4 h and then was
quenched with 0.1 M hydrochloric acid (10 mL). The result-
ing mixture was extracted with diethyl ether (3 · 10 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–ethyl acetate (5:1) as eluent).

Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
4745
3.4.1. Diallylmethylphenylsilane (6a)
IR: mmax (liquid film) 3072.5, 2971.3, 2916.2, 1630.0,
4.98–5.02 (4H, t, 2 · CH2@), 2.09–2.11 (4H, d, 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). Anal. Calc. C12H15ClSi: C, 64.69; H, 6.79; Si,
12.61. Found: C, 64.76; H, 6.76; Si, 12.55%.
1
1426.9, 1252.1, 1154.2, 1113.2 cmÀ1; H 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,
2 · CH2CH@CH2), 0.28 (3H, s, CH3); 13C NMR (100
MHz, CDCl3): d 136.71, 134.05, 133.79, 129.06, 127.62,
113.73, 21.44, À5.98; MS: m/z (%): 202 (M+, 2.1), 161
(100), 121 (30.5), 105 (11.9).
3.5.3. Allyldichlorophenylsilane (9a)
IR: mmax (liquid film) 3070.6, 2969.1, 1630.0, 1427.9,
1112.5 cmÀ1 1H NMR (400 MHz, CDCl3): d 7.28–7.72
;
3.4.2. Diallyldiphenylsilane (6b)
IR: mmax (liquid film) 3069.6, 2998.2, 1629.9, 1427.9,
(5H, m, ArH), 5.73–5.83 (1H, m, CH), 5.05–5.09 (2H, t,
CH2@), 2.30–2.32 (2H, d, CH2CH@CH2); 13C NMR
(100 MHz, CDCl3): d 133.96, 131.77, 130.82, 130.53,
128.13, 115.66, 19.40; MS: m/z (%): 216 (M+, 19.92), 175
(100), 77 (22.14).
1
1110.8, 907.9, 732.7 cmÀ1; H NMR (400 MHz, CDCl3):
d 7.32–7.52 (10H, m, ArH), 5.78 (2H, m, 2 · CH), 4.86–
4.94 (4H, t, 2 · CH2@), 2.11–2.13 (4H, d, 2 · CH2-
CH@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).
3.5.4. Triallylmethylsilane (7b)
IR: mmax (liquid film) 3078.0, 2971.8, 2919.9, 1630.5,
1
1254.3, 1159.2, 895.3 cmÀ1; H NMR (400 MHz, CDCl3):
3.4.3. Diallylmethylvinylsilane (6c)
IR: mmax (liquid film) 3053.7, 2922.1, 2850.7, 1631.1,
d 5.71–5.87 (3H, m, 3 · CH), 4.84–4.94 (6H, m,
3 · CH2@), 1.55–1.66 (6H, m, 3 · CH2CH@CH2), 0.40
(3H, s, CH3); 13C NMR (100 MHz, CDCl3): d 134.34,
113.47, 20.80, À6.24; MS: m/z (%): 166 (M+, 1.96), 125
(100).
1
1407.1, 1258.6, 1062.3, 892.6 cmÀ1; H NMR (400 MHz,
CDCl3): d 5.99–6.12 (2H, m, 2 · CH), 5.69–5.83 (3H, m,
CH@CH2), 4.85–4.90 (4H, m, 2 · CH2@), 1.62–1.64 (4H,
d, 2 · CH2CH@CH2), 0.08 (3H, s, CH3); 13C NMR
(100 MHz, CDCl3): d 136.28, 134.29, 132.99, 113.50,
21.34, À6.13; MS: m/z (%): 152 (M+, 0.56), 111 (100), 83
(33.8).
3.6. The reaction of perchlorosilane (SiCl4) with
allylsamarium bromide
Allylsamarium bromide was added to a THF solution of
perchlorosilanes (SiCl4), the respective amounts depending
upon the desired allyl chlorosilanes. After the addition was
completed the mixture was stirred for 30 min under room
temperature. The inorganic precipitate was filtered off
and washed repeatedly with dry ether. The filtrate was then
freed from any solvent and the residual liquid fractionally
distilled.
3.5. The reaction of trichlorosilanes (RSiCl3) with
allylsamarium bromide
Allylsamarium bromide was added to a THF solution of
trichlorosilanes (RSiCl3), the respective amounts depend-
ing upon the desired allyl chlorosilanes. After the addition
was completed the mixture was stirred for 1–2 h under
room temperature. The inorganic precipitate was filtered
off and washed repeatedly with dry ether. The filtrate was
then freed from any solvents and the residual liquid frac-
tionally distilled.
3.6.1. Tetraallylsilane (10)
IR: mmax (liquid film) 3077.6, 2972.8, 2919.3, 2882.9,
;
1630.8, 1163.2, 991.6, 930.2, 896.1 cmÀ1 1H NMR
(400 MHz, CDCl3): d 5.73–5.87 (4H, m, 4 · CH), 4.87–
4.97 (8H, m, 4 · CH2@), 1.60–1.68 (8H, m, 4 ·
CH2CH@CH2); 13C NMR (100 MHz, CDCl3): 133.12,
114.54, 21.99; MS: m/z (%): 192 (M+, 3.26), 151 (81.93),
123 (100), 95 (93.68), 69 (35.87).
3.5.1. Triallylphenylsilane (7a)
IR: mmax (liquid film) 3075.1, 2998.1, 2971.7, 2922.1,
2854.1, 1630.0, 1425.7, 1156.9, 1111.8, 1029.7 cmÀ1 1H
;
NMR (400 MHz, CDCl3): d 7.34–7.52 (5H, m, ArH),
5.73–5.84 (3H, m, 3 · CH), 4.87–4.94 (6H, t, 3 · CH2@),
1.85–1.87 (6H, d, 3 · CH2CH@CH2); 13C NMR (100
MHz, CDCl3): d 135.22, 134.25, 133.87, 129.39, 127.79,
114.35, 19.55; MS: m/z (%): 228 (M+, 5.64), 187 (67.37),
159 (100), 145 (73.68), 105 (58.00). Anal. Calc. C15H20Si:
C, 78.88; H, 8.83; Si, 12.30. Found: C, 78.76; H, 8.76; Si,
12.25%.
3.6.2. Triallylchlorosilane (11)
Colorless liquid; bp 96–97 ꢁC (30 mmHg); 1H NMR
(400 MHz, CDCl3): d 5.76–5.90 (3H, m, 3 · CH), 4.89–
4.99 (6H, m, 3 · CH2@), 1.65–1.73 (6H, m, 3 ·
CH2CH@CH2); MS: m/z (%): 186 (M+, 2.21), 145
(79.83), 104 (100).
3.5.2. Diallylchlorophenylsilane (8a)
3.6.3. Diallyldichlorosilane (12)
IR: mmax (liquid film) 3073.0, 3002.4, 2974.2, 2919.8,
1632.0, 1428.9, 1121.7 cmÀ1; 1H NMR (400 MHz, CDCl3):
d 7.33–7.47 (5H, m, ArH), 5.74–5.82 (2H, m, 2 · CH),
Colorless liquid; bp 64–66 ꢁC (26 mmHg); 1H NMR
(400 MHz, CDCl3): d 5.77–5.91 (2H, m, 2 · CH), 4.88–
4.98 (4H, m, 2 · CH2@), 1.66–1.74 (4H, m, 2 ·

4746
Z. Li et al. / Journal of Organometallic Chemistry 691 (2006) 4740–4746
CH2CH@CH2); MS: m/z (%): 180 (M+, 1.31), 139 (80.83),
98 (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: Asymmetry 15 (2004)
2647.
3.6.4. Allyltrichlorosilane (13)
1
Colorless liquid; bp 116–118 ꢁC; H NMR (400 MHz,
[5] (a) For reviews see B. Marciniec, C. Pietraszuk, Curr. Org. Chem. 7
(2003) 691;
CDCl3): d 5.75–5.98 (1H, m, CH), 4.88–4.99 (2H, m,
CH2@), 1.68–1.77 (2H, m, CH2CH@CH2); MS: m/z (%):
174 (M+, 2.24), 133 (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, Wein-
heim, VCH, 2002 (Chapter 2.6);
Acknowledgements
(d) J.A. Reichl, D.H. Berry, Adv. Organomet. Chem. 43 (1998) 203;
(e) B. Marciniec, Appl. Organomet. Chem. 14 (2000) 527.
[6] (a) M. Jankowska, O. Shuvalova, N. Bespalova, M. Majchrzak, B.
Marciniec, J. Organomet. Chem. 690 (2005) 4492;
(b) B. Marciniec, D. Chadyniak, S. Krompiec, J. Mol. Catal. A:
Chem. 224 (2004) 111;
We are grateful to the Natural Science Foundation of
Zhejiang Province (Project No. Y404380) for financial
support.
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