Synthesis of mono-, di-, and trisilyl-substituted alkenes via the hydrosilylation of methylenecyclopropanes catalyzed by Rh(I) complexes

Full text of DOI:10.1021/jo961536z

J . Org. Chem. 1997, 62, 6069-6076
6069
lyzed by the Wilkinson complex, which was published in
our preliminary communication.5
Now we present the results of the hydrosilylation of
methylenecyclopropanes 1-7 with various silanes.
Syn th esis of Mon o-, Di-, a n d
Tr isilyl-Su bstitu ted Alk en es via th e
Hyd r osilyla tion of Meth ylen ecyclop r op a n es
Ca ta lyzed by Rh (I) Com p lexes
A. G. Bessmertnykh, K. A. Blinov, Yu. K. Grishin,
N. A. Donskaya, E. V. Tveritinova, N. M. Yur‘eva, and
I. P. Beletskaya*
Department of Chemistry, Moscow State University,
Moscow, 119899, Russia
Received August 7, 1996 (Revised Manuscript Received J une 17,
1997 )
In tr od u ction
Transition metal catalyzed hydrosilylation of alkenes
and alkynes is an efficient and economical route to
organosilanes.1 In reality the hydrosilylation reaction is
a rather complex process because in every case the results
obtained depend on many factors such as catalyst,
temperature, the nature of silane and substrate. There-
fore, some types of organosilanes are almost inaccessible.
In the present work we have focused our attention on
the synthesis of mono-, di-, and trisilylated olefins, which
are interesting as monomers and intermediates for
organic synthesis. We suggested the use methylenecy-
clopropanes as a starting material, because the hydrosi-
lylation of polyunsaturated compounds is known to
proceed nonselectively with formation of complex mix-
tures of products.1b,2 During the last decade methyl-
enecyclopropanes have become available and found ap-
plication in organic synthesis as versatile building blocks.3
Though numerous metal catalyzed reactions of meth-
ylenecyclopropanes are known,4 only some of them are
sufficiently selective to be used as synthetic methods. To
our knowledge, hydrosilylation of methylenecyclopro-
panes has never been mentioned in the literature, with
the only exception being the reaction of phenyl-substi-
tuted methylenecyclopropanes with triethylsilane cata-
All selected hydrocarbons contain either tri- or tetra-
substituted double bonds. Though polysubstituted olefins
are often reluctant to participate in the hydrosilylation
reaction, these strained molecules readily underwent
hydrosilylation. Hydrosilylation of methylenecyclopro-
panes 1-4 resulted in the cleavage of cyclopropane ring,
leading to monosilylated olefins. The hydrosilylation
reaction of methylenecyclopropanes 5-7 containing two
reactive fragments, the methylenecyclopropane and vi-
nylcyclopropane6 moieties, lead to di- and trisilylated
olefins.
Both H2PtCl6 (Speier catalyst) and Rh(I) complexes
including tris(triphenylphosphine)rhodium chloride, bis-
(triphenylphosphine)carbonylrhodium chloride and di-µ-
chlorotetrakis(η2-methylenecyclopropane)dirhodium, which
we have recently prepared,8 were used as catalysts.
Resu lts a n d Discu ssion
All olefins 1-7 were found to be unreactive toward
silanes in the presence of the Speier catalyst, tradition-
ally used for hydrosilylation of alkenes.
The reaction of methylenecyclopropanes 1-4 with
various silanes catalyzed by the Wilkinson complex
proceeds selectively with the cleavage of the C1-C2 bond
of the cyclopropane ring to produce â-silyl-substituted
alkenes in good yields.
(1) (a) Speier, J . L. Adv. Organomet. Chem. 1979, 17, 407. (b)
Armitage, D. A. In Comprehensive Organometallic Chemistry; Wilkin-
son, G., Stone, F. G. A., Abel, E. W., Eds.; Oxford: University Press:
New York, 1982, vol. 2, pp 117-120. (c) Lukevics, E.; Belyakova, Z.
V.; Pomerantseva, M. G.; Voronkov, M. G. Organometallic Chemistry
Reviews. In J ournal of Organometallic Chemistry Library; Seyferth,
D., Davies, A. G., Fisher, E. O., Normant J . F., Reutov, O. A., Eds.;
Elsevier: Amsterdam, 1977; vol. 5.
(2) (a) Kakiuchi, F.; Nogami, K.; Chatani, N.; Seki, Y.; Murai, S.
Organometallics 1993, 12, 4748-4750. (b) Green, M.; Spenses, J . L.;
Stone, F. G. A.; Tsipis, K. A. J . Chem. Soc., Dalton Trans. 1977, 1519-
1525.
(3) (a) Binger, P.; Buech, M. Top. Curr. Chem. 1987, 135, 77-151.
(b) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1-20. (c) De
Meijere, A.; Wessjohann, L. Synlett 1990, 20-32.
(4) (a) Noyori, R.; Odagi, T.; Takaya, H. J . Am. Chem. Soc. 1970,
92, 5780-5781. (b) Noyori, R.; Kumagai, Y.; Umeda, I.; Takaya, H. J .
Am. Chem. Soc. 1972, 94, 4018-4020. (c) Binger, P.; Cetinkaya, M.;
Doyl, M. J .; Germer, A.; Shushard, U. In Fundamental Research in
Homogeneous Catalysis; Plenum Press: New York, 1979, Vol. 3, pp
271-284. (d) Balme, G.; Fournet, G.; Gore, J . Tetrahedron Lett. 1986,
27, 3855-3858. (e) Fournet, G.; Balme, G.; Gore, J . Tetrahedron Lett.
1987, 28, 4533-4536. (f) Chiusoli, G. P.; Costa, M.; Schianchi, P.;
Salerno, G. J . Organomet. Chem. 1986, 315, C45-C50. (g) Chiusoli,
G. P.; Costa, M.; Pivetti, F. J . Organomet. Chem. 1989, 373, 377-384.
(h) Stolle, A.; Salaun, J .; De Meijere, A. Tetrahedron Lett. 1990, 31,
4593-4596. (i) Lewis, R. T.; Motherwell, W. B.; Shipman, M. J . Chem.
Soc., Chem. Commun. 1988, 948-950. (j) Yamago, S.; Nakamura, E.
J . Chem. Soc., Chem. Commun. 1988, 1112-1113. (k) Motherwell, W.
B.; Shipman, M. Tetrahedron Lett. 1991, 32, 1103-1106. (l) Lautens,
M.; Reh, Y.; Delanghe, P. H. M. J . Am. Chem. Soc. 1994, 116, 8821-
8823. (m) Chatani, N.; Takeyasu, T.; Hanafusa, T. Tetrahedron Lett.
1988, 29, 3979-3982.
Monoaryl-substituted methylenecyclopropanes 1, 2
react with triethylsilane at room temperature to give
silylated styrenes 8a , 9a in quantitative yields (Table 1,
entries 1, 4).
(5) Bessmertnykh, A. G.; Grishin, Yu. K.; Donskaya, N. A.; Be-
letskaya, I. P. Metalloorg. Khim. 1993, 6, 30-35.
(6) Recently we have found that the hydrosilylation of vinylcyclo-
propane catalyzed by Rh(PPh3)3Cl results in the addition to the
cyclopropane ring to produce silylated olefins.7
(7) Bessmertnykh, A. G.; Blinov, K. A.; Grishin, Yu. K.; Donskaya,
N. A.; Beletskaya, I. P. Tetrahedron Lett. 1995, 36, 7901-7905.
(8) (a) Donskaya, N. A.; Yur‘eva, N. M.; Beletskaya, I. P. Mendeleev
Commun. 1992, 136-137. (b) Donskaya, N. A.; Yur‘eva, N. M.;
Voevodskaya, T. I.; Sigeev, A. S.; Beletskaya, I. P. Zh. Org. Khim. 1994,
30, 801-806.
S0022-3263(96)01536-8 CCC: $14.00 © 1997 American Chemical Society

6070 J . Org. Chem., Vol. 62, No. 17, 1997
Ta ble 1. Hyd r osilyla tion of Meth ylen ecyclop r op a n es 1-4
Notes
The increase of steric hindrance in methylenecyclo-
propane 3 due to the presence of two phenyl substituents
at the double bond leads to a decrease in the hydrosilyl-
ation rate. The reaction of olefin 3 with triethylsilane
was examined by varying the catalyst and temperature
(Table 1, entries 7-11). The best yield of â-silylated
olefin 10a is achieved in the presence of Rh(PPh3)3Cl or
Rh(CO)Cl(PPh3)2 at 80 °C. The catalytic activity of
Rh(CO)Cl(PPh3)2 was lower than that of the Wilkinson
catalyst.
the hydrosilylation of 4 can be performed selectively with
the formation of only 11.
The use of di-µ-chlorotetrakis(η2-methylenecyclopro-
pane)dirhodium, which is more effective than the Wilkin-
son catalyst,8 promotes the formation of 11 selectively
in high yield even at room temperature (Table 1, entry
14).
It is noteworthy that the nature of the silane has no
influence on the structure of hydrosilylation products
formed from compounds 1-39 though the reaction rates
and product yields are sensitive to the structure of silane.
The reactivity of silanes decreased in the order Et3SiH
Cyclopropylidenecyclohexane 4, lacking aryl substitu-
ents, is the least reactive of the methylenecyclopropanes
examined. This compound fails to react with triethylsi-
lane in the presence of the Wilkinson complex at room
temperature, but reacts at 80 °C in 0.5 h to afford a
mixture of three silylated olefins in the ratio of 1:1:1 (as
1
measured by H NMR). At lower temperature (50 °C)

Notes
J . Org. Chem., Vol. 62, No. 17, 1997 6071
Sch em e 1
methylenecyclopropane fragment is always observed, a
cyclopropane ring may survive the reaction conditions.
We have developed methods for the selective formation
of mono- and disilylated olefins. The ratio of mono- and
disilylated products is almost independent on the reaction
time or temperature,12 but strongly depends on the
nature of silane and ligand in Rh catalyst.
The use of triethylsilane and Rh(CO)Cl(PPh3)2 as a
catalyst produces only disilylsubstituted compounds 18,
19 in good yields (Scheme 2). Only a selective cleavage
of the methylenecyclopropane fragment occurs in the
hydrosilylation of compounds 5, 6 with less reactive
triethoxysilane. â-Silylated alkenes 20, 21 were obtained
in good yields. The reactions catalyzed by the Wilkinson
catalyst and Rh(CO)Cl(PPh3)2 require elevated temper-
atures (Table 2). Complex [(C4H6)2RhCl]2 was found to
be more efficient catalyst for this transformation and
allows the reaction to be performed at room temperature
(Table 2, entries 4, 8).
A quite unusual result was obtained in the reaction of
(dicyclopropylmethylene)cyclopropane (7) with triethyl-
silane in the presence of the Wilkinson complex (Scheme
2). Two products are formed in this case in the ratio 2.3:1
(GC). They were isolated by distillation and character-
ized by NMR and elemental analyses data. The former
is established to be disilylated olefin 24 (56% yield), in
which the methylenecyclopropane moiety remained in-
tact, in contrast to reactions of compounds 5, 6 (Table 2,
entry 9). The second product is trisilylated olefin 23. The
ratio of 24:23 is almost constant in the reaction course
and independent of the conversion. The compound 24
was shown not to react with triethylsilane in the presence
of Wilkinson complex at room temperature. It means
that compound 23 did not form via 24, and there are two
independent paths of hydrosilylation of methylenecyclo-
propane 7.
Conditions for selective hydrosilylation of 7 leading to
either of mono- or trisilylated compounds have been
established. The use of triethylsilane and [(C4H6)2RhCl]2
as catalyst provides preparation of only trisilylated olefin
23 in 73% yield (Table 2, entry 10). Hydrosilylation of 7
with less reactive triethoxysilane leads to monosilylated
product 22 (Table 2, entry 11), analogous to reaction
involving compounds 5, 6.
For compounds 5-7 the reaction seems to include the
formation of complexes in which the methylenecyclopro-
pane is coordinated to the rhodium atom at different sites
within the molecule, e.g., the double bond, the vinylcy-
clopropane fragment, or the cyclopropane substituents
(in 7).
g PhMe2SiH > (EtO)3SiH . Me2ClSiH. For example,
the hydrosilylation of methylenecyclopropanes 1-3 with
Et3SiH and PhMe2SiH proceeds at room temperature, but
the reaction with less reactive triethoxysilane proceeds
only at 80 °C in the presence of the Wilkinson complex
(Table 1). Methyldichlorosilane and trichlorosilane fail
to react with 1-3 even at 80-100 °C in the presence of
any of the catalysts utilized.
Some conclusions on the mechanism may be derived
from the analysis of the reaction products. For methyl-
enecyclopropanes 1-4, the classic catalytic cycle of
Chalk-Harrod10 can be considered as a background. The
(cyclopropylmethyl)rhodium intermediate A (see Scheme
1) is formed by the migratory insertion of the CdC bond
into the Rh-H bond. We propose, however, that in this
case the cyclopropylmethyl-3-butenyl rearrangement of
A to the open-chain intermediate B leads to the C1-C2
bond cleavage.
The hydrosilylation of 1, 2 is not stereoselective
because the isomerization of Z-isomer of 8a -c and 9a -c
to a more stable E-isomer 8a -c and 9a -c is observed in
the course of the reaction.
The hydrosilylation of compounds 1-3 is accompanied
by a partial reduction to yield 1-phenyl-1-butene (13),
1-(p-methoxyphenyl)-1-butene (14), and 1,1-diphenyl-1-
butene (15), correspondingly,11 although yields do not
exceed 5-7% in the case of triethyl- or dimethylphenyl-
silane. However, the hydrosilylation 3 with the less
reactive triethoxysilane in the presence of the Wilkinson
catalyst at 80 °C generates reduction product in 43%
yield.
The hydrosilylation of cyclopropyl-substituted meth-
ylenecyclopropanes 5-7 containing several reactive sites
is more complicated. The structure of reaction products
was found to depend on the silane and catalyst.
Con clu sion s. The hydrosilylation of methylenecyclo-
propanes catalyzed by Rh(I) complexes presents a useful
preparative route to â-silylated olefins. The reaction of
cyclopropyl-substituted methylenecyclopropanes may be
accomplished selectively to give alkenes containing one,
two, or even three silyl groups.
(9) In the hydrosilylation of vinylcyclopropanes the structure of the
reaction products depends on the nature of silane.7
(10) Chalk, A. J .; Harrod, J . F. J . Am. Chem. Soc. 1965, 87, 16-21.
(11) The structure of the compounds 13-15 was determined in
comparison with authentic samples prepared by hydrogenation of the
methylenecyclopropanes 1-3 in the presence of the Wilkinson catalyst.
(12) The amount of more stable isomers of mono- (16, 18) and
disilylated (17, 19) olefins increased on prolonged contact with catalyst
retained in the reaction mixture, as observed for hydrosilylation of
compounds 1, 2. The isomerization of the double bond in the final
products was also observed in the case of the methyl-substituted
methylenecyclopropane 5.
Methylenecyclopropanes 5 and 6 react with an excess
of triethylsilane in the presence of the Wilkinson complex
to produce a mixture of mono- and disilylated alkenes
16, 18 (in the ratio of 1:1) and 17, 19 (in the ratio of 1:1),
respectively (Table 2). Thus, while ring-opening in the

6072 J . Org. Chem., Vol. 62, No. 17, 1997
Notes
Ta ble 2. Hyd r osilyla tion of Meth ylen ecyclop r op a n es 5-7
otherwise indicated. IR spectra were recorded with a UR-20
infrared spectrometer. The Mass spectrum was recorded on
a Finnigan MAT-112S.
Exp er im en ta l Section
Gen er a l P r oced u r e. All manipulations were carried out
under argon using syringe techniques. Solvents were freshly
distilled under argon prior to use. Olefins were distilled over
CaH2 and degassed. All starting compounds were no less than
95% pure (by GC analysis). GC analyses were carried out on
a Tsvet-530 gas chromatograph (thermoconductivity detector)
equipped with packed silicone elastomer SE 30 on Chromaton
N-AW column (2 mm × 3 m). Silica gel column chromatog-
raphy was carried out with silica Silpearl 40/100.
P r ep a r a t ion of t h e St a r t in g Com p ou n d s. (Phenyl-
methylene)cyclopropane (1),13 [(p-methoxyphenyl)methyl-
ene]cyclopropane (2),14 (diphenylmethylene)cyclopropane (3),13
cyclopropylidenecyclohexane (4),15 (1-methyl-1-cyclopropyl-
methylene)cyclopropane (5),16 (1-phenyl-1-cyclopropylmethyl-
(13) Utimoto, K.; Tamura, M.; Sisido, K. Tetrahedron 1973, 29,
1169-1171.
(14) Salaun, J .; Hanack, M. J . Org. Chem. 1975, 40, 1994-1998.
1H and 13C NMR spectra were recorded on a Varian VXR-
400 spectrometer in CDCl3 (internal standard CHCl3) unless

Notes
J . Org. Chem., Vol. 62, No. 17, 1997 6073
Sch em e 2
ene)cyclopropane (6),17 and (dicyclopropylmethylene)cyclo-
propane (7)16 were obtained by means of the reported proce-
dures.
(2C), 16.38, 22.94, 126.44, 127.76, 127.83 (2C), 128.15 (2C),
128.75 (2C), 128.96, 133.61 (2C), 135.64, 137.67, 139.05. (E)-
8b: 1H NMR δ 0.58 (6H, s), 1.21 (2H, m), 2.62 (2H, m), 6.47
(1H, m), 6.55 (1H, m), 7.3-7.5 (5H, m), 7.55 (2H, m), 7.78 (3H,
m). 13C NMR δ -2.95 (2C), 15.46, 27.42, 125.98 (2C), 126.77,
127.86 (2C), 128.50 (2C), 128.61, 128.96, 133.40, 133.65 (2C),
Tris(triphenylphosphine)rhodium chloride18 and bis(tri-
phenylphosphine)carbonylrhodium chloride19 were synthesized
by means of published standard procedures. Di-µ-chlorotet-
rakis(η2-methylenecyclopropane)dirhodium was obtained as in
ref 8b.
137.95, 139.14. IR (neat): 1250, 1605, 1660 cm-1
. Anal.
Calcd for C18H22Si: C 81.13, H 8.32. Found: C 80.60; H 8.20.
4-(Tr ieth oxysilyl)-1-p h en yl-1-bu ten e (8c) (a m ixtu r e of
Z-/E-isom er s in th e r a tio of 1:2). 8c was prepared as a
colorless liquid from 1.00 g (7.7 mmol) of 1 and 1.38 g (8.4
mmol) of triethoxysilane at 80 °C for 10 h in the yield of 0.93
g (41%) after distillation: bp 95-100 °C/0.05 mmHg. (Z)-8c:
1H NMR δ 0.89 (2H, m), 1.34 (9H, t, J ) 7.0 Hz), 2.55 (2H, m),
3.92 (6H, q, J ) 7.0 Hz), 5.82 (1H, dt, J ) 11.9 Hz, J ) 7.2
Hz), 6.48 (1H, d, J ) 11.9 Hz), 7.23 (1Hp, m), 7.36 (2Hm, m),
7.45 (2Ho, m). 13C NMR δ 10.87, 18.20 (3C), 21.95, 58.22 (3C),
126.29 (2C), 127.80, 127.85, 127.94 (2C), 134.97, 137.05. (E)-
8c: 1H NMR δ 0.92 (2H, m), 1.28 (9H, t, J ) 7.0 Hz), 2.43
(2H, m), 3.93 (6H, q, J ) 7.0 Hz), 6.38 (1H, dt, J ) 15.9 Hz, J
) 6.7 Hz), 6.61 (1H, d, J ) 15.9 Hz), 7.24 (1Hp, m), 7.35 (2Hm,
m), 7.41 (2Ho, m). 13C NMR δ 10.20, 18.20 (3C), 26.21, 58.22
(3C), 125.82 (2C), 126.61, 128.29 (2C), 128.61, 132.71, 137.77.
Anal. Calcd for C16H26O3Si: C 65.26; H 8.90; Si 9.54. Found:
C 64.85; H 8.60; Si 9.03.
Hyd r osilyla tion of th e Com p ou n d s 1-4 Ca ta lyzed by
th e Wilk in son Com p lex. (Gen er a l P r oced u r e). A Schlenk
tube equipped with a magnetic stirring bar and a septum was
charged with the Wilkinson complex (0.1 mol %) evacuated
and filled with argon three times. Anhydrous toluene (10 mL)
and silane (5.1 mmol) were added into the reactor via a
syringe. The mixture was stirred for 5 min to produce a
homogeneous solution. Methylenecyclopropane (5.0 mmol)
was added via a syringe. The reaction mixture was stirred
under the conditions shown in Table 1 until the starting
compounds disappeared. The solvent was evaporated under
reduced pressure, and the residue was passed through short
column of SiO2 (eluent hexane) to separate the catalyst. The
reaction products were isolated by column chromatography
(SiO2) or distilled in vacuo.
4-(Tr ieth ylsilyl)-1-p h en yl-1-bu ten e (8a ) (a m ixtu r e of
Z-/E-isom er s in th e r a tio of 1:3). 8a was prepared as a
colorless oil from 0.65 g (5.0 mmol) of 1 and 0.59 g (5.1 mmol)
of triethylsilane in 20 h at rt in the yield of 1.17 g (95%). The
isomers were isolated by column chromatography (eluent
pentane-ethyl acetate 10:1). (Z)-8a : 1H NMR δ 0.57 (6H, q,
J ) 8.0 Hz), 0.76 (2H, m), 0.98 (9H, t, J ) 8.0 Hz), 2.37 (2H,
m), 5.75 (1H, dt, J ) 11.3 Hz, J ) 7.3 Hz), 6.39 (1H, d, J )
11.3 Hz), 7.28 (1Hp, m), 7.30 (2Ho, m), 7.38 (2Hm, m). 13C NMR
δ 3.23 (3C), 7.30 (3C), 12.01, 22.77, 126.27, 127.30, 127.99 (2C),
4-(Tr ieth ylsilyl)-1-(p-m eth oxyp h en yl)-1-bu ten e (9a ) (a
m ixtu r e of Z-/E-isom er s in th e r a tio of 3:1). 9a was
prepared as a colorless oil from 0.80 g (5.0 mmol) of 2 and
0.59 g (5.1 mmol) of triethylsilane at rt for 20 h in the yield of
1.32 g (96%). The isomers were separated by column chro-
matography (eluent pentane-ethyl acetate 10:1). (Z)-9a : 1H
NMR δ 0.57 (6H, q, J ) 8.0 Hz), 0.75 (2H, m), 0.98 (9H, t, J )
8.0 Hz), 2.36 (2H, m), 3.85 (3H, s), 5.65 (1H, dt, J ) 11.6 Hz,
J ) 7.2 Hz), 6.31 (1H, d, J ) 11.6 Hz), 6.70 (2H, HA,HA′ of
1
128.60 (2C), 136.12, 137.72. (E)-8a : H NMR δ 0.60 (6H, q, J
) 8.0 Hz), 0.76 (2H, m), 1.00 (9H, t, J ) 8.0 Hz), 2.15 (2H, m),
6.31 (1H, dt, J ) 15.7 Hz, J ) 6.9 Hz), 6.41 (1H, d, J ) 15.7
Hz), 7.21 (1Hp, m), 7.32 (2Hm, m), 7.39 (2Ho, m). 13C NMR δ
3.44 (3C), 7.53 (3C), 11.20, 27.44, 125.98 (2C), 126.74, 128.31,
128.53 (2C), 134.01, 138.10. IR (neat): 740, 1240, 1500, 1600
cm-1. Anal. Calcd for C16H26Si: C 77.97; H 10.63. Found: C
77.91; H 10.84.
AA′BB′, J app ) 8.5 Hz), 7.38 (2H, HB,HB′ of AA′BB′, J app
)
8.5 Hz). 13C NMR δ 3.32 (3C), 7.48 (3C), 12.14, 22.90, 55.22,
113.53 (2C), 126.81 (2C), 129.89, 130.47, 134.72, 158.11. (E)-
9a : 1H NMR δ 0.57 (6H, q, J ) 8.0 Hz), 0.65 (2H, m), 0.98
(9H, t, J ) 8.0 Hz), 2.15 (2H, m), 3.75 (3H, s), 6.08 (1H, dt, J
) 15.9 Hz, J ) 6.9 Hz), 6.29 (1H, d, J ) 15.9 Hz), 6.75 (2H,
HA,HA′ of AA′BB′, J app ) 8.5 Hz), 7.20 (2H, HB,HB′ of AA′BB′,
J app ) 8.5 Hz). 13C NMR δ 3.32 (3C), 7.48 (3C), 11.21, 27.22,
55.24, 113.89 (2C), 126.92 (2C), 127.49, 130.85, 131.88, 158.46.
IR (neat): 1250, 1610 1660 cm-1. Anal. Calcd for C17H28OSi:
C 73.85; H 10.21; Si 10.16. Found: C 74.36; H 10.41; Si 9.42.
4-(Dim et h ylp h en ylsilyl)-1-(p -m et h oxyp h en yl)-1-b u -
ten e (9b) (a m ixtu r e of Z-/E-isom er s in th e r a tio of 2:3).
9b was prepared as a colorless oil from 0.40 g (2.5 mmol) of 2
and 0.40 g (3.0 mmol) of dimethylphenylsilane for 10 h at 20
°C in the yield of 0.70 g (88%). The isomers were separated
by column chromatography (eluent pentane-ethyl acetate 10:
1). (Z)-9b: 1H NMR δ 0.46 (6H, s), 1.19 (2H, m), 2.62 (2H,
m), 3.85 (3H, s), 6.38 (1H, m), 6.55 (1H, m), 7.18 (2H, HA,HA′
4-(Dim eth ylp h en ylsilyl)-1-p h en yl-1-bu ten e (8b) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:2). 8b was prepared
as a colorless liquid from 1.00 g (7.7 mmol) of 1 and 1.27 g
(9.3 mmol) of dimethylphenylsilane in 20 h at rt in the yield
of 1.69 g (83%) after distillation: bp 173 °C/2 mmHg. (Z)-8b:
1H NMR δ 0.54 (6H, s), 1.21 (2H, m), 2.51 (2H, m), 5.95 (1H,
dt, J ) 11.8 Hz, J ) 7.4 Hz), 6.58 (1H, d, J ) 11.8 Hz), 7.3-
7.5 (5H, m), 7.55 (2H, m), 7.73 (3H, m). 13C NMR δ -2.86
(15) Schweitzer, E. E.; Berninger, C. J .; Thompson, J . J . J . Org.
Chem. 1968, 33, 336-339.
(16) Akhachinskaya, T. V.; Bakhbukh, M.; Grishin, Yu. K.; Don-
skaya, N. A.; Ustynyuk, Yu. A. Zh. Org. Khim. 1978, 14, 2317-2323.
(17) Dunkelblum, E. Tetrahedron 1974, 30, 3991-3996.
(18) Osborn, J . A.; J ardine, F. H.; Young, J . F.; Wilkinson, G. J .
Chem. Soc. A 1966, 1711-1732.
of AA′BB′, J app ) 8.4 Hz), 7.45 (2H, HB,HB′ of AA′BB′, J app
)
8.4 Hz), 7.58 (3H, m), 7.68 (2H, m). 13C NMR δ -2.96 (2C),
16.42, 22.91, 55.25, 113.56 (2C), 127.15 (2C), 127.63 (2C),

6074 J . Org. Chem., Vol. 62, No. 17, 1997
Notes
127.92, 128.84, 130.45, 130.55, 133.64 (2C), 139.16, 158.09.
(E)-9b: 1H NMR δ 0.49 (6H, s), 1.21 (2H, m), 2.44 (2H, m),
3.82 (3H, s), 5.85 (1H, dt, J ) 15.9 Hz, J ) 7.0 Hz), 6.57 (1H,
d, J ) 15.9 Hz), 6.95 (2H, HA,HA′ of AA′BB′, J app ) 8.4 Hz),
7.52 (2H, HB,HB′ of AA′BB′, J app ) 8.4 Hz), 7.58 (3H, m), 7.68
(2H, m). 13C NMR δ -2.89 (2C), 15.58, 27.35, 55.25, 113.93
(2C), 127.02, 127.83, 128.92 (2C), 129.91 (2C), 130.77, 130.93,
133.64 (2C), 139.26, 158.63.
4-(Tr ieth oxysilyl)-1-(p-m eth oxyp h en yl)-1-bu ten e (9c)
(a m ixtu r e of Z-/E-isom er s in th e r a tio of 1:5). 9c was
obtained as a colorless oil from 2.50 g (15.6 mmol) of 2 and
3.28 g (20.0 mmol) of triethoxysilane at 80 °C for 50 h in the
yield of 3.29 g (65%) after distillation: bp 130-132 °C/0.05
mmHg. (Z)-9c: 1H NMR δ 0.66 (2H, m), 1.20 (9H, t, J ) 7.0
Hz), 2.43 (2H, m), 3.77 (3H, s), 3.80 (6H, q, J ) 7.0 Hz), 5.61
(1H, dt, J ) 12.0 Hz, J ) 7.1 Hz), 6.28 (1H, d, J ) 12.0 Hz),
6.82 (2H, HA,HA′ of AA′BB′, J app ) 8.4 Hz), 7.20 (2H, HB,HB′
of AA′BB′, J app ) 8.4 Hz). 13C NMR δ 11.13, 18.34 (3C), 22.87,
55.32, 58.36 (3C), 113.54 (2C), 127.34, 129.25 (2C), 129.95,
133.30, 158.18. (E)-9c: 1H NMR δ 0.81 (2H, m), 1.22 (9H, t,
J ) 7.0 Hz), 2.30 (2H, m), 3.81 (3H, s), 3.82 (6H, q, J ) 7.0
Hz), 6.14 (1H, dt, J ) 15.7 Hz, J ) 6.6 Hz), 6.31 (1H, d, J )
15.7 Hz), 6.81 (2H, HA,HA′ of AA′BB′, J app ) 8.4 Hz), 7.25
(2H, HB,HB′ of AA′BB′, J app ) 8.4 Hz). 13C NMR δ 10.45, 18.34
(3C), 26.26, 55.32, 58.36 (3C), 113.87 (2C), 127.00 (2C), 128.13,
129.35, 130.71, 158.69.
rated under reduced pressure, and the residue was passed
through short column with SiO2 to separate the catalyst. The
reaction products were isolated by column chromatography
(eluent pentane) or distillation in vacuo.
(E)-1-P h en yl-1-bu ten e (13).5,20 13 was prepared from 0.55
g (4.2 mmol) of 1 and isolated in 44% yield by column
chromatography (eluent pentane) from a mixture with butyl-
benzene. 1H NMR δ 1.11 (3H, t, J ) 7.4 Hz), 2.25 (2H, m),
6.29 (1H, dt, J ) 15.7 Hz, J ) 6.6 Hz), 6.43 (1H, d, J ) 15.7
Hz), 7.20 (1H, m), 7.33 (4H, m); 13C NMR δ 13.66, 26.07,
125.88 (2C), 126.73, 128.45 (2C), 128.75, 132.64, 137.91.
1-(p-Meth oxyp h en yl)-1-bu ten e (14)5,21 (a m ixtu r e of Z-/
E-isom er s in th e r a tio of 1:4). 14 was prepared from 0.1 g
(0.5 mmol) of 2 and isolated in 50% yield by column chroma-
tography (eluent pentane-ethyl acetate 10:1) from a mixture
with p-buthylanisole. (Z)-14 1H NMR δ 1.08 (3H, t, J ) 7.4
Hz), 2.36 (2H, m), 3.83 (3H, s), 5.59 (1H, dt, J ) 11.6 Hz, J )
7.1 Hz), 6.34 (1H, d, J ) 11.6 Hz), 6.85 (2H, HA,HA′ of AA′BB′,
J app ) 8.4 Hz), 7.22 (2H, HB,HB′ of AA′BB′, J app ) 8.4 Hz).
13C NMR δ 14.60, 22.02, 55.34, 113.56 (2C), 127.68, 129.95
1
(2C), 130.40, 133.20, 158.16. (E)-14 H NMR δ 1.10 (3H, t, J
) 7.4 Hz), 2.23 (2H, m), 3.82 (3H, s), 6.17 (1H, dt, J ) 15.9
Hz, J ) 7.0 Hz), 6.34 (1H, d, J ) 15.9 Hz), 6.83 (2H, HA,HA′
of AA′BB′, J app ) 8.5 Hz), 7.30 (2H, HB,HB′ of AA′BB′, J app
)
8.4 Hz). 13C NMR δ 13.86, 26.10, 55.29, 113.93 (2C), 127.00
(2C), 128.14, 130.55, 130.81, 158.61.
1,1-Dip h en yl-1-bu ten e (15).5,22 15 was prepared from 0.50
g (2.4 mmol) of 3 for 20 h in quantitative yield: bp 110 °C/1
mmHg. 1H NMR δ 1.02 (3H, t, J ) 7.3 Hz), 2.11 (2H, m), 6.06
(1H, t, J ) 7.0 Hz), 7.25 (10H, m). 13C NMR δ 14.51, 23.18,
126.72, 126.82, 127.21 (2C), 128.04 (2C), 128.09 (2C), 129.89
(2C), 131.71, 140.24, 140.97, 142.82.
Hyd r osilyla tion of 5-7 Ca ta lyzed by th e Wilk in son
Com p lex. (Gen er a l P r oced u r e). A Schlenk tube equipped
with magnetic stirrer and a septum was charged with the
Wilkinson complex (0.8 mol %) and then evacuated and filled
with argon three times.
Anhydrous toluene (10 mL) and silane (25.0 mmol) were
introduced via syringe. The mixture was stirred for 5 min to
produce a homogeneous solution. Then methylenecyclopro-
pane (5.0 mmol) was added. The reaction mixture was stirred
under the conditions shown in Table 2 until the starting
compounds disappeared. The solvent was evaporated under
reduced pressure, the residue was passed through short
column of SiO2 (eluent hexane) to remove the catalyst. The
reaction products are isolated by column chromatography or
distillation in vacuo.
5-(Tr ieth ylsilyl)-2-cyclop r op yl-2-p en ten e (16) a n d 1,7-
Bis(tr ieth ylsilyl)-4-m eth yl-3-h ep ten e (18). 16 and 18 were
obtained in the ratio 1:1 from 0.30 g (3.0 mmol) of 5 and 0.80
g (7.0 mmol) of triethylsilane for 3 d at rt in overall yield of
1.0 g (88%). The reaction mixture was distilled. The com-
pounds 16 and 18 were additionally purified by column
chromatography (eluent hexane).
4-(Tr ieth ylsilyl)-1,1-d ip h en yl-1-bu ten e (10a ) was ob-
tained from 0.50 g (2.4 mmol) of 3 and 0.29 g (2.5 mmol)
triethylsilane at rt for 65 h in the yield of 0.65 g (84%) after
the column chromatography (eluent pentane-ethyl acetate
10:1): 1H NMR δ 0.47 (6H, q, J ) 8.0 Hz), 0.69 (2H, m), 0.88
(9H, t, J ) 8.0 Hz), 2.11 (2H, m), 5.85 (1H, t, J ) 7.6 Hz), 7.21
(2H, m), 7.28 (4H, m), 7.39 (4H, m). 13C NMR δ 3.37 (3C),
7.50 (3C), 12.09, 24.17, 126.75, 126.90, 127.27 (2C), 128.15
(2C), 128.18 (2C), 130.00 (2C), 133.07, 140.08, 140.28, 142.96.
IR (neat): 730, 1240, 1610 cm-1
.
4-(Tr ieth oxysilyl)-1,1-d ip h en yl-1-bu ten e (10c) a n d 1,1-
Dip h en yl-1-bu ten e (15) (a m ixtu r e 4:5). The reaction of
0.42 g (2.0 mmol) of 3 with 0.34 g (2.2 mmol) of triethoxysilane
at 80 °C for 40 h leads to a mixture of 10c and 15. They were
separated by column chromatography (eluent pentane) and
distilled.
4-(Tr ieth oxysilyl)-1,1-d ip h en yl-1-bu ten e (10c). Yield of
10c was 0.25 g (34%): bp 142-143 °C/0.01 mmHg. 1H NMR
δ 0.83 (2H, m), 1.23 (9H, t, J ) 7.0 Hz), 2.27 (2H, m), 3.79
(6H, q, J ) 7.0 Hz), 6.20 (1H, t, J ) 7.5 Hz), 7.2-7.4 (10H, m).
13C NMR δ 11.08, 18.35 (3C), 23.16, 58.40 (3C), 126.47, 126.82,
127.29 (2C), 128.12 (2C), 128.20 (2C), 130.00 (2C), 132.06,
140.17, 140.64, 142.83. IR (neat): 710, 770, 1090, 1115, 1600,
1665, 1715 cm-1
.
1,1-Dip h en yl-1-bu ten e (15). Yield of 15 was 0.18 g
(43%): bp 132-133 °C/8 mmHg. The spectral characteristics
coincided with the authentic sample.
[2-(Tr ieth ylsilyl)p r op ylid en e]cycloh exa n e (11). 11 was
prepared from 0.60 g (4.9 mmol) of 4 and 0.58 g (5.0 mmol) of
triethylsilane at 50 °C for 1 h in the yield of 0.97 g (82%) after
distillation: bp 54-55 °C/3 mmHg. 1H NMR δ 0.54 (6H, q, J
) 8.0 Hz), 0.59 (2H, m), 0.96 (9H, t, J ) 8.0 Hz), 1.54 (6H, m),
2.01 (2H, m), 2.07 (2H, m), 2.14 (2H, m), 5.13 (1H, t, J ) 7.4
Hz). 13C NMR δ 3.44 (3C), 7.46 (3C), 12.27, 21.27, 27.06, 27.84,
28.58, 28.63, 37.18, 124.80, 137.86.
5-(Tr ieth ylsilyl)-2-cyclop r op yl-2-p en ten e (16) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:4). Bp 134 °C/14
mmHg. (Z)-16 1H NMR δ 0.51 (4H, m), 0.52 (6H, q, J ) 8.0
Hz), 0.63 (2H, m), 0.93 (9H, t, J ) 8.0 Hz), 1.39 (3H, m), 1.64
(1H, m), 2.15 (2H, m), 5.26 (1H, t, J ) 6.9 Hz). 13C NMR δ
3.40 (3C), 3.83 (2C), 7.45 (3C), 11.95, 12.19, 18.77, 21.63,
1
129.36, 132.91. (E)-16 H NMR δ 0.42 (2H, m), 0.51 (2H, m),
At room temperature the starting compounds remain un-
changed. The catalyst was transformed into an insoluble
orange complex.
0.52 (6H, q, J ) 8.0 Hz), 0.58 (2H, m), 0.94 (9H, t, J ) 8.0
Hz), 1.34 (1H, m), 1.49 (3H, m), 2.00 (2H, m), 5.23 (1H, t, J )
6.8 Hz). 13C NMR δ 3.40 (3C), 4.09 (2C), 7.45 (3C), 11.79,
13.76, 18.68, 22.08, 126.57, 133.76.
Three isomeric olefins (1H NMR data) are formed at 80 °C
for 0.5 h: bp 54-56 °C/3 mmHg. Identification of isomers was
not carried out.
1,7-Bis(tr ieth ylsilyl)-4-m eth yl-3-h ep ten e (18) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:7). Bp 135 °C/2
Hyd r ogen a tion of 1-3 Ca ta lyzed by th e Wilk in son
Com p lex. (Gen er a l P r oced u r e). A Schlenk tube equipped
with the septum was charged with the Wilkinson complex (2
mol %) evacuated and filled with hydrogen three times. Then
anhydrous benzene (10 mL) was placed into the reactor via a
syringe. The mixture was stirred to produce a homogeneous
solution. Then methylenecyclopropane (5.0 mmol) was added.
The reaction mixture was stirred at room temperature until
the starting compound disappeared. The solvent was evapo-
1
mmHg. (Z)-18 H NMR δ 0.51 (6H, q, J ) 8.0 Hz), 0.52 (4H,
(19) Colquhoun, H. M.; Holton, J .; Thompson, D. J .; Twigg, M. V.
New Pathways for Organic Synthesis; Plenum Press: 1985, p 381.
(20) Hauser, C. F.; Brooks, T. W.; Miles, M. L.; Raymond, M. A.;
Butler, G. B. J . Org. Chem. 1963, 28, 372-379.
(21) Le Bigot, Y.; Delmas, M.; Gaset, A. Synth. Commun. 1982, 12,
1115-1116.
(22) Schmidt, A. W.; Hartmann, C. Chem. Ber. 1941, 74, 1325-1332.

Notes
J . Org. Chem., Vol. 62, No. 17, 1997 6075
m), 0.52 (6H, q, J ) 8.0 Hz), 0.93 (9H, t, J ) 8.0 Hz), 0.94
(9H, t, J ) 8.0 Hz), 1.35 (2H, m), 1.56 (3H, m), 2.00 (4H, m),
5.16 (1H, t, J ) 6.9 Hz) 13C NMR δ 3.48 (3C), 3.54 (3C), 7.58
(6C), 11.51, 12.35, 22.11, 22.51, 23.47, 35.96, 128.91, 133.75.
ated and filled with argon three times. Then anhydrous
pentane (5 mL), the freshly prepared complex (0.1 mol %), and
silane (5.0-20.0 mmol) were placed in the tube by means of a
syringe. The mixture was stirred for 5 min to produce a
homogeneous solution. Then methylenecyclopropane (5.0
mmol) was added. The reaction mixture was stirred at room
temperature until the starting compounds disappeared. The
solvent was evaporated under reduced pressure, and the
residue was distilled in vacuo or passed through short column
with SiO2 (eluent hexane).
1
(E)-18 H NMR δ 0.51 (6H, q, J ) 8.0 Hz), 0.52 (2H, m), 0.52
(6H, q, J ) 8.0 Hz), 0.58 (2H, m), 0.93 (9H, t, J ) 8.0 Hz),
0.94 (9H, t, J ) 8.0 Hz), 1.35 (2H, m), 1.65 (3H, m), 2.00 (4H,
m), 5.19 (1H, t, J ) 7.0 Hz). 13C NMR δ 3.48 (3C), 3.54 (3C),
7.58 (6C), 11.09, 11.95, 15.78, 22.27, 29.87, 44.02, 128.11,
133.54.
4-(Tr ieth oxysilyl)-1,1-d ip h en yl-1-bu ten e (10c). 10c was
prepared from 0.40 g (2.0 mmol) of 3 and 0.33 g (2.0 mmol) of
triethoxysilane for 10 h in the yield 0.44 g (60%).
Hydrosilylation of 5 at 80 °C for 8 h leads to the formation
of a mixture (1:1) of 16 (a m ixtu r e of Z-/E-isom er s in th e
r a tio of 1:1) and 18 (a m ixtu r e of Z-/E-isom er s in th e r a tio
of 1:9) in 89% yield.
[[2-(Tr iet h ylsilyl)p r op ylid en e]cycloh exa n e (11). 11
was prepared from 0.61 g (5.0 mmol) of 4 and 1.16 g (10.0
mmol) of triethylsilane for 2 h in the yield of 11 of 1.08 g (91%).
5-(Tr ieth oxysilyl)-2-cyclop r op yl-2-p en ten e (20) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:2). 20 was prepared
from 1.54 g (14.0 mmol) of 5 and 7.05 g (43.0 mmol) of
triethoxysilane for 2 h in the yield of 2.98 g (78%): bp 104-
106 °C/1 mmHg. (Z)-20 1H NMR δ 0.54 (2H, m), 0.61 (2H,
m), 0.77 (2H, m), 1.26 (9H, t, J ) 7.0 Hz), 1.42 (3H, m), 1.69
(1H, m), 2.28 (2H, m), 3.86 (6H, q, J ) 7.0 Hz), 5.29 (1H, t, J
) 6.9 Hz). 13C NMR δ 3.62 (2C), 10.81, 11.98, 18.08 (3C),
4-(Tr ieth ylsilyl)-1-cyclop r op yl-1-p h en yl-1-bu ten e (17)
a n d 1,7-Bis(tr ieth ylsilyl)-4-p h en yl-3-h ep ten e (19). A mix-
ture of 17 and 19 in the ratio of 1:1 was prepared from 0.51 g
(3.0 mmol) of 6 and 1.74 g (15.0 mmol) of triethylsilane for 3
d at rt in 84% overall yield. The reaction mixture was distilled.
4-(Tr iet h ylsilyl)-1-cyclop r op yl-1-p h en yl-1-b u t en e (a
m ixtu r e of Z-/E-isom er s in th e r a tio of 1:1) (17). Yield of
17 was 0.32 g (37%): bp 109-110 °C/0.01 mmHg. (Z)-17 1H
NMR δ 0.42 (6H, q, J ) 8.0 Hz), 0.55 (2H, m), 0.64 (4H, m),
0.85 (9H, t, J ) 8.0 Hz), 1.57 (1H, m), 1.90 (2H, m), 5.48 (1H,
t, J ) 6.9 Hz), 7.18-7.35 (5H, m). 13C NMR δ 3.27 (3C), 5.15
(2C), 7.36 (3C), 12.11, 18.31, 23.06, 126.44, 127.81 (2C), 128.74,
128.77 (2C), 140.08, 140.51. (E)-17 1H NMR δ 0.30 (2H, m),
0.58 (6H, q, J ) 8.0 Hz), 0.64 (2H, m), 0.72 (2H, m), 0.98 (9H,
t, J ) 8.0 Hz), 1.71 (1H, m), 2.39 (2H, m), 5.74 (1H, t, J ) 6.8
Hz), 7.18-7.35 (5H, m). 13C NMR δ 3.41 (3C), 6.56 (2C), 7.51
(3C), 11.33, 11.54, 22.69, 126.06, 127.22 (2C), 127.69 (2C),
135.02, 138.81, 142.75.
1,7-Bis(tr ieth ylsilyl)-4-p h en yl-3-h ep ten e (a m ixtu r e of
Z-/E-isom er s in th e r a tio of 1:2) (19). Yield of 19 was 0.57
g (47%): bp 168-170 °C/0.01 mmHg. (Z)-19 1H NMR δ 0.44
(6H, q, J ) 8.0 Hz), 0.47 (6H, q, J ) 8.0 Hz), 0.52 (2H, m),
0.60 (2H, m), 0.87 (9H, t, J ) 8.0 Hz), 0.89 (9H, t, J ) 8.0 Hz),
1.32 (2H, m), 1.94 (2H, m), 2.35 (2H, t, J ) 7.5 Hz), 5.48 (1H,
t, J ) 7.3 Hz), 7.14 (2Ho, m), 7.21 (1Hp, m), 7.36 (2Hm, m). 13C
NMR δ 3.29 (6C), 7.37 (3C), 7.45 (3C), 10.77, 12.27, 22.28,
23.08, 43.07, 126.20,127.86 (2C), 128.36 (2C), 130.58, 139.25,
141.42. (E)-19 1H NMR δ 0.48 (6H, q, J ) 8.0 Hz), 0.53 (4H,
m), 0.58 (6H, q, J ) 8.0 Hz), 0.89 (9H, t, J ) 8.0 Hz), 0.99
(9H, t, J ) 8.0 Hz), 1.70 (2H, m), 2.22 (2H, m), 2.52 (2H, t, J
) 7.5 Hz), 5.72 (1H, t, J ) 7.1 Hz), 7.14 (2Ho, m), 7.23 (1Hp,
m), 7.33 (2Hm, m). 13C NMR δ 3.32 (3C), 3.40 (3C), 7.42 (3C),
7.51 (3C), 11.39, 12.01, 22.90, 29.74, 33.79, 126.27 (3C), 128.10
(2C), 132.43, 138.39, 143.43. Anal. Calcd for C25H46Si2: C
74.55, H 11.51. Found: C 73.78, H 11.80.
1
18.60, 20.46, 58.02 (3C), 128.23, 133.16. (E)-20 H NMR δ 0.45
(2H, m), 0.56 (2H, m), 0.72 (2H, m), 1.26 (9H, t, J ) 7.0 Hz),
1.37 (1H, m), 1.51 (3H, m), 2.15 (2H, m), 3.85 (6H, q, J ) 7.0
Hz), 5.27 (1H, t, J ) 6.9 Hz). 13C NMR δ 3.88 (2C), 10.67,
13.54, 18.08 (3C), 18.49, 20.90, 58.02 (3C), 125.39, 134.06. IR
(neat): 1090, 1120, 1660, 1720 cm-1
.
4-(Tr ieth oxysilyl)-1-cyclopr opyl-1-ph en yl-1-bu ten e (21)
(a m ixtu r e of Z-/E-isom er s in th e r a tio of 1:2). 21 was
prepared from 0.40 g (2.3 mmol) of 6 and 1.15 g (7.0 mmol) of
triethoxysilane for 4 d in the yield of 0.64 g (81%): bp 109-
1
111 °C/0.05 mmHg. (Z)-21 H NMR δ 0.45 (2H, m), 0.63 (2H,
m), 0.69 (2H, m), 1.20 (9H, t, J ) 7.0 Hz), 1.60 (1H, m), 2.03
(2H, m), 3.75 (6H, q, J ) 7.0 Hz), 5.54 (1H, t, J ) 6.9 Hz),
7.18 (2Ho, m), 7.24 (1Hp, m), 7.35 (2Hm, m). 13C NMR δ 5.06
(2C), 11.18, 18.24 (3C), 18.33, 22.10, 58.22 (3C), 126.45, 127.74
(2C), 127.83 (2C), 128.82, 140.26, 140.83. (E)-21 1H NMR δ
0.34 (2H, m), 0.82 (2H, m), 0.86 (2H, m), 1.29 (9H, t, J ) 7.0
Hz), 1.76 (1H, m), 2.56 (2H, m), 3.90 (6H, q, J ) 7.0 Hz), 5.79
(1H, t, J ) 6.9 Hz), 7.18 (2Ho, m), 7.27 (1Hp, m), 7.32 (2Hm,
m). 13C NMR δ 6.59 (2C), 10.61, 11.35, 18.34 (3C), 21.78, 58.37
(3C), 126.13, 127.21 (2C), 127.67 (2C), 134.00, 139.47, 142.46.
IR (neat): 1080, 1115, 1230, 1600, 1620, 1640 cm-1
. Mass
spectrum (EI, 70 eV) m/ z: 334 (2%) (M+), 163 (100%), 135
(29%), 131 (15%), 119 (60%), 115 (42%), 107 (18%), 91 (31%),
79 (66%).
4-(Tr ieth oxysilyl)-1,1-d icyclop r op yl-1-bu ten e (22). 22
was prepared from 0.50 g (3.7 mmol) of 7 and 2.13 g (13.0
mmol) of triethoxysilane for 2 h in the yield of 0.74 g (66%):
[Bis[3-(t r iet h ylsilyl)p r op yl]m et h ylen e]cyclop r op a n e
(24) a n d 4-[3-(tr ieth ylsilyl)p r op yl]-1,7-bis(tr ieth ylsilyl)-
3-h ep ten e (23). A mixture of 24 and 23 in the ratio of 2.3:1
was obtained from 1.15 g (8.6 mmol) of 7 and 4.86 (42.0 mmol)
of triethylsilane for 3 d at rt in 80% overall yield. The reaction
mixture was distilled.
1
bp 91-93 °C/0.05 mmHg; H NMR δ 0.23 (2H, m), 0.42 (2H,
m), 0.56 (2H, m), 0.65 (2H, m), 0.66 (2H, m), 0.85 (1H, m),
1.17 (9H, t, J ) 7.0 Hz), 1.58 (1H, m), 2.20 (2H, m), 3.78 (6H,
q, J ) 7.0 Hz), 5.10 (1H, t, J ) 6.7 Hz); 13C NMR δ 4.33 (2C),
4.66 (2C), 10.84, 12.33, 12.74, 18.23 (3C), 20.52, 59.23 (3C),
[Bis[3-(t r iet h ylsilyl)p r op yl]m et h ylen e]cyclop r op a n e
(24). Yield was 24 was 1.75 g (56%): bp 139-140 °C/0.02
mmHg; 1H NMR δ 0.51 (12H, q, J ) 8.0 Hz), 0.61 (4H, m),
0.91 (18H, t, J ) 8.0 Hz), 0.99 (4H, m), 1.52 (4H, m), 2.15 (4H,
t, J ) 7.6 Hz). 13C NMR δ 1.97 (2C), 3.40 (6C), 7.49 (6C), 11.47
(2C), 22.28 (2C), 39.20 (2C), 114.97, 128.31; IR (neat): 1020,
1240, 1610, 1780 cm-1. Anal. Calcd for C22H46Si2: C 72.24,
H 12.60, Si 15.29. Found: C 72.04, H 12.64, Si 15.31.
4-[3-(Tr ieth ylsilyl)p r op yl]-1,7-bis(tr ieth ylsilyl)-3-h ep -
ten e (23). Yield of 23 was 0.99 g (24%): bp 180-182 °C/0.01
mmHg; 1H NMR δ 0.50 (4H, m), 0.51 (12H, q, J ) 8.0 Hz),
0.52 (6H, q, J ) 8.0 Hz), 0.59 (2H, m), 0.93 (18H, t, J ) 8.0
Hz), 0.94 (9H, t, J ) 8.0 Hz), 1.37 (4H, m), 1.92 (2H, m), 2.02
(4H, m), 5.15 (1H, t, J ) 6.9 Hz); 13C NMR δ 3.56 (3C), 3.60
(6C), 7.58 (9C), 11.40, 11.82, 12.45, 22.15, 22.83, 23.13, 34.48,
125.94, 138.25. IR (neat): 1090, 1130, 1600, 1660, 1730 cm-1
.
4-[3-(Tr ieth ylsilyl)p r op yl]-1,7-bis(tr ieth ylsilyl)-3-h ep -
ten e (23). 23 was prepared from 0.50 g (3.7 mmol) of 7 and
2.32 g (20.0 mmol) of triethylsilane for 2 h in the yield of 1.31
g (73%).
Hyd r osilyla tion of 5-7 Ca ta lyzed by Rh (CO)(P P h 3)2Cl.
(Gen er a l P r oced u r e). A Schlenk tube equipped with a
magnetic stirring bar and a septum was charged with the
Rh(CO)(PPh3)2Cl (0.8 mol %), evacuated, and filled with argon
three times. Then anhydrous toluene (10 mL) and silane (25.0
mmol) were added into the reactor via a syringe. The mixture
was stirred for 5 min to produce a homogeneous solution.
Methylenecyclopropane (5.0 mmol) was added via a syringe.
The reaction mixture was stirred at 80 °C until the starting
compounds disappeared. The solvent was evaporated under
reduced pressure, and the residue was distilled in vacuo or
passed through column with SiO2.
41.47, 128.60, 137.86. IR (neat): 1175, 1240, 1615, 1670 cm-1
.
Anal. Calcd for C28H62Si3: C 69.62, H 12.94, Si 17.44.
Found: C 70.18, H 12.51, Si 16.94.
Hyd r osilyla tion Ca ta lyzed by Di-µ-ch lor otetr a k is[η2-
m et h ylen ecyclop r op a n e]d ir h od iu m . A Schlenk tube
equipped with a magnetic stirrer and the septum was evacu-
4-(Tr ieth ylsilyl)-1,1-d ip h en yl-1-bu ten e (10a ). 10a was
obtained from 0.31 g (1.5 mmol) of 3 and 1.16 g (3.7 mmol)
triethylsilane at room temperature for 10 d in the yield of 0.42

6076 J . Org. Chem., Vol. 62, No. 17, 1997
Notes
g (88%). It was refined by column chromatography (eluent
pentane-ethyl acetate 10:1).
prepared from 0.40 g (2.4 mmol) of 6 and 1.15 g (7.0 mmol) of
triethoxysilane for 5 h at 80 °C in the yield of 0.56 g (71%):
bp 121-122 °C/0.1 mmHg.
4-(Tr ieth ylsilyl)-1,1-d ip h en yl-1-bu ten e (10a ). 10a was
obtained from 0.10 g (0.05 mmol) of 3 and 0.15 g (1.25 mmol)
of triethylsilane at 80 °C for 5 h in the yield of 0.15 g (96%).
1,7-Bis(tr ieth ylsilyl)-4-m eth ylh ep t-3-en e (18) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:4). 18 was prepared
from 0.78 g (7.2 mmol) of 5 and 5.77 mL (36.0 mmol) of
triethylsilane at 80 °C for 3 h in the yield of 2.1 g (86%), 90%
purity (GC), after passing through a short column with SiO2
(eluent pentane).
Ack n ow led gm en t. We thank The International
Science Foundation (Grant M 5O300) and The Russian
Foundation of Fundamental Research (Grant 96-03-
34231a) for financial support.
Su p p or tin g In for m a tion Ava ila ble: Tables and copies of
1H NMR and 13C spectra for compounds 8b, 8c, 9b, 9c, 10a ,
10c, 11, 16, 17, 18, 20-22 (9 pages). This material is contained
in libraries on microfiche, immediately follows this article in
the microfilm version of the journal, and can be ordered from
the ACS; see any current masthead page for ordering
information.
1,7-Bis(tr ieth ylsilyl)-4-p h en yl-3-h ep ten e (19) (a m ix-
tu r e of Z-/E-isom er s in th e r a tio of 1:1). 19 was prepared
from 0.51 g (3.0 mmol) of 6 and 1.74 g (15.0 mmol) of
triethylsilane for 3 h at 80 °C in the yield of 0.73 g (60%): bp
168-170 °C/0.01 mmHg.
4-(Tr ieth oxysilyl)-1-cyclopr opyl-1-ph en yl-1-bu ten e (21)
(a m ixtu r e of Z-/E-isom er s in th e r a tio of 1:1). 21 was
J O961536Z