The efficient method for the preparation of alkenylsilanes from organoaluminums

Article abstract of DOI:10.1016/j.jorganchem.2014.04.004

Silyl esters of sulfonic acids are convenient and efficient silylating agents for β,β- and β-substituted 1-alkenylaluminums. The reaction proceeds at room temperature in CH₂Cl₂ or hexane for 18 h to give corresponding alkenylsilanes in high yield. At the same time, α,β-disubstituted and α,β,β-trisubstituted 1-alkenylaluminums were inert in the reaction under study. The reaction with aluminacyclopen-2-enes and aluminacyclopentanes takes place on the less sterically hindered reaction center. Using electron-donating solvents (diethyl ether, THF) inhibits the reaction. A new convenient procedure of silylation was developed, which consists in obtaining the silyl tosylate by the reaction of chlorosilanes with anhydrous sodium tosylate in toluene solution. The resulting reaction mixture was reacted with organoaluminum compounds without isolation of silyl tosylate.

Full text of DOI:10.1016/j.jorganchem.2014.04.004

Accepted Manuscript
The efficient method for the preparation of alkenylsilanes from organoaluminums
Rita N. Kadikova, Tat’yana P. Zosim, Usein M. Dzhemilev, Ilfir R. Ramazanov
PII:
S0022-328X(14)00174-0
10.1016/j.jorganchem.2014.04.004
JOM 18539
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 27 November 2013
Revised Date: 27 March 2014
Accepted Date: 1 April 2014
Please cite this article as: R.N. Kadikova, T.’y.P. Zosim, U.M. Dzhemilev, I.R. Ramazanov, The
efficient method for the preparation of alkenylsilanes from organoaluminums, Journal of Organometallic
Chemistry (2014), doi: 10.1016/j.jorganchem.2014.04.004.
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1
ACCEPTED MANUSCRIPT
Silyl esters of sulfonic acids are efficient silylating agents for β,β- and β-substituted
1-alkenylaluminums. A new convenient procedure of silylation was developed, which
consists in obtaining the silyl tosylate by the reaction of chlorosilanes with anhydrous
sodium tosylate in toluene solution.

ACCEPTED MANUSCRIPT
Graphical abstract
silyl ester of
sulfonic asid
hydro- or carbo-
alumination
R
R'
R
R'
R
R'
or
R''
R''
al
si
TMSCl - TsONa
R= alkyl; R' = H;
R'' = H or alkyl, aryl
80-90%
al = AlMe2, AlEt2, Al(i-Bu)2
si = SiMe3, SiMe2Ph

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ACCEPTED MANUSCRIPT
The efficient method for the preparation of alkenylsilanes
from organoaluminums
Rita N. Kadikova, Tat’yana P. Zosim, Usein M. Dzhemilev, Ilfir R. Ramazanov*
Institute of Petrochemistry and Catalysis of Russian Academy of Sciences, 141
Prospekt Oktyabrya, Ufa 450075, Russian Federation
Tel./fax: +7-347-284-2750. E-mail address: iramazan@inbox.ru
Abstract
Silyl esters of sulfonic acids are convenient and efficient silylating agents for β,β- and
β-substituted 1-alkenylaluminums. The reaction proceeds at room temperature in
CH2Cl2 or hexane for 18 hours to give corresponding alkenylsilanes in high yield. At
the same time, α,β-disubstituted and α,β,β-trisubstituted 1-alkenylaluminums were
inert in the reaction under study. The reaction with aluminacyclopen-2-enes and
aluminacyclopentanes takes place on the less sterically hindered reaction center.
Using electron-donating solvents (diethyl ether, THF) inhibits the reaction. A new
convenient procedure of silylation was developed, which consists in obtaining the
silyl tosylate by the reaction of chlorosilanes with anhydrous sodium tosylate in
toluene solution. The resulting reaction mixture was reacted with organoaluminum
compounds without isolation of silyl tosylate.
Keywords: alkenylaluminums, silylation, silyl esters of sulfonic acids.
1. Introduction
The reaction of organometallic compounds with chlorosilanes is one of the general
methods of formation of carbon-silicon bond [1,2]. Despite the fact that the first
organosilicon compounds were prepared by Friedel and Crafts by the reaction of
dialkylzinc with tetrachlorosilane [3], nowdays the organolithium and -magnesium
compounds are more widely used in the synthesis of substituted silanes. Recently it
was found that silver [4], copper [5] and zinc [6] salts catalyze the reaction of
chlorosilanes with aryl- and alkenyl Grignard reagents. Organic derivatives of sodium
and of aluminum are used to a much lesser extent. For example, it is known that
sodium reacts with halogenated aromatic compounds and chlorosilanes in a manner
analogous to the Wurtz–Fittig reaction [7]. The reaction of aluminum alkyl halides
with SiCl4 at a temperature of 350-450 ° C gives the alkyl substituted silanes [8]. At
the same time, very few examples of the alkylation of halogenated silanes with
organoaluminum compounds are known. Me3SiCl was obtained in 88% yield by the
treatment of Me2SiCl2 with Me3Al at 60 °C [9]. The alkylation of SiF4 by lower
alkylaluminums at 325-375 ° C and a pressure of 250 psi was described [10]. There is
an example of silylation of trans-3,4-dialkylsubstituted aluminacyclopentanes by
dichloro(methyl)vinylsilane which gives substituted silacyclopentanes with 50-60 %
yield [11]. Thus, the preparative methods for the conversion of organoaluminum
compounds into alkenylsilanes are missing and very few examples of the silylation of
higher alkylaluminums are known. It is noteworthy that alkenyl derivatives of
aluminum can be obtained by hydro-, carbo- and cycloalumination of alkynes and

2
ACCEPTED MANUSCRIPT
some transformations are easily feasible only in the case of the organoaluminum
compounds.
2. Results and discussion
Negishi methylalumination is one of the most useful transformations of alkynes [12].
However we have found that alkenylaluminums prepared in this way [13] do not react
with chlorosilanes. Carrying out the reaction at 50 oC for 18 hours did not result in the
formation of expected alkenylsilanes. Earlier we have demonstrated the efficiency of
the use of alkyl esters of sulfonic acids for the alkylation of cyclic alkenylaluminums
(aluminacyclopen-2-enes) [14,15]. High yields of the resulting cyclopropanes and
selectivity of the transformation called our attention to the prospects of using the
derivatives of sulfonic acids for the functionalization of organoaluminum compounds.
It is possible that esters of sulfonic acids react with organoaluminum compounds
through the formation of a less strained six-membered transition state. Moreover, silyl
esters of sulfonic acids are stronger electrophilic agents than TMSCl. The global
electrophilicity index [16], calculated using 6-31G(d), is decreasing in the series:
TfOTMS (0.47)> (TMSO)2SO2 (0.34)> MsOTMS (0.33)> TMSCl (0.30). From the
above, we assumed that the organosilicon derivatives of sulfonic acids may be
effective agents for silylation of organoaluminium compounds. Thus, in order to
develop effective method for the synthesis of alkenylsilanes, we have studied the
reactions of acyclic and cyclic alkenylaluminums with (TMSO)2SO2, MsOTMS,
TsOTMS, TfOTMS and MsOSiMe2Ph.
We have found that Zr-catalyzed methylalumination of terminal alkynes
(1-octyne, 1-decyne, phenylacetylene) [13] followed by treatment with 6 equivalents
of MsOTMS in CH2Cl2 solution at room temperature for 18 hours afforded substituted
1-alkenylsilanes 1a-c with E-configuration of the double bond in high yield (82-93%)
(Scheme 1). Using electron-donating solvents (diethyl ether, THF) inhibits the
reaction.
The addition of trimethylsilyl group takes place with preservation of the
configuration of the double bond that was confirmed by the presence of cross-peaks
between the hydrogen atom at the double bond and the α-hydrogen atoms of n-C6H13
and n-C8H17 groups in NOESY spectra of 1a, b. It should be noted that all aluminium-
carbon bonds of organoaluminum compounds (including unreacted in first stage
Me3Al) were involved in the silylation reaction, so 6 equivalents of silylating agent
was required to complete the conversion. A number of silyl esters of sulfonic acids
were tested. The yields of compound 1a using (TMSO)2SO2, TsOTMS, PhSO2OTMS
and TfOTMS as silylating agents are 80-94%, which are close to the result obtained in
the case of MsOTMS. The reaction with MsOSiMe2Ph gave alkenylsilane 1d in 86%
yield.
Due to the simplicity of the procedure and the efficiency of silyl esters of sulfonic
acids as silylating agents, we examined this methodology for the functionalization of
alkenylaluminums of different structure. Alkyl substituted terminal alkynes can be
readily converted to β-substituted 1-alkenylaluminums under the action of DIBAL-H
[17]. Further reaction of resulting organoaluminum compounds with one equivalent of
silyl esters of methanesulfonic acid (MsOTMS, MsOSiMe2Ph) gave the
corresponding alkenylsilanes 2a, b in high yields (88, 81%) (Scheme 2). Note that it is
enough to use only one equivalent of silylating agent to complete the conversion.
Presumably, iso-butyl group at aluminum atom is less reactive toward silyl esters of

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ACCEPTED MANUSCRIPT
sulfonic acids. Phenylacetylene reacts with DIBAL-H to yield mainly
alkynylaluminum formed by metallation of the terminal alkyne [18]. The addition of
one equivalent of MsOTMS produces trimethyl(2-phenylethynyl)silane in 66% yield.
Ti-catalyzed hydroalumination [19] and the Zr-catalyzed methylalumination of 5-
decyne [13] gives α,β-disubstituted, and α,β,β−trisubstituted 1-alkenylaluminums
which were inert towards to MsOTMS (Scheme 3). Obviously the steric factor plays
an important role in the reaction under investigation. Bulk trimethylsilyl group is
experiencing considerable steric hindrance to the approach to the reaction center due
to the interaction with α-positioned n-butyl substituent of alkenylaluminum.
Zr-Catalyzed reaction of
disubstituted alkynes with Et3Al gives
aluminacyclopent-2-enes which are a particular case of α,β,β-substituted 1-
alkenylaluminums [20]. As expected, the reaction of 2,3-dialkyl substituted
aluminacyclopent-2-enes with 3 equivalents of silyl esters of methanesulfonic acid
(MsOTMS, MsOSiMe2Ph) involves only Al-C(sp3) bond of metallacycle to give
organosilicon alkenes 3a-c with 84-89% yield after deuterolysis (Scheme 4).
Apparently, the low reactivity of the Al-C(sp2) bond of aluminacyclopent-2-enes
caused by the same factors that have prevented the formation of alkenylsilanes in the
case of α,β−disubstituted and α,β,β-trisubstituted 1-alkenylaluminums on Scheme 3.
As the functionalization of aluminacyclopent-2-enes involved only Al-C(sp3)
bond of metallacycle, it was interesting to examine aluminacyclopentanes in the
reaction under study. Zr-catalyzed cycloalumination of 1-octene and styrene [21]
followed by subsequent treatment with silyl esters of methylsulfonic acid (MsOTMS,
MsOSiMe2Ph) gave compounds 4a,b with high yield after quenching with H2O or
D2O (Scheme 5). Only less hindered Al-C bond of aluminacycle was involved in the
reaction that allows the futher functionalization of the other Al-C bonds. For example,
sequential treatment of 2-ethyl-3-n-hexylaluminacyclopentane with MsOTMS and O2
yielded 2-[2-(trimethylsilyl)ethyl]-1-octanol 5 in 85% yield.
In order to simplify the silylation procedure, we have developed a new method,
which consists in obtaining the silyl tosylate by the reaction of chlorosilanes with
sodium tosylate in toluene solution. The resulting reaction mixture was reacted with
organoaluminum compounds without isolation of silyl tosylate. The first stage of the
o
procedure takes only 5 minutes at 110 C. When used one and a half-fold excess of
chlorosilanes, the product yields were almost similar to those observed with isolated
silyl esters.
The developed method provides some benefits in the preparation of
tetraorganosilanes. While β-substituted silanes can be prepared in good yields by
hydroalumination of alkynylsilanes, the obtaining of β,β-substituted silanes presents a
problem. For example, alkenylsilane 1a had previously been obtained by the reaction
of 1-octyne with Me3SiI and Me2Zn in the presence of Pd(PPh3)4 in 48-57% yield
[22]. Our approach gives the same silane in 94% yield. The developed procedures are
especially useful for the identification of organoaluminium compounds. Currently, the
deuterolysis and iodinolysis (to some extent) are common procedures that are used for
establishing their structure. To our best knowledge, despite the obviousness,
simplicity, and effectiveness of the proposed procedures, our work presents the first
example of the silylation of organoaluminums under the action of silyl esters of
sulfonic acids.
3. Conclusions

4
ACCEPTED MANUSCRIPT
Thus, we have proposed an efficient method for the preparation of alkenylsilanes from
unsaturated organoaluminum compounds under the action of silyl esters of sulfonic
acids.
4. Experimental
4.1. General Procedures
The reagents were obtained from Aldrich or Acros. Dichloromethane and hexane
were distilled over P2O5. (TMSO)2SO2 was prepared by heating of sulfuric acid with
TMSCl for 1h at 50 °C [23]. Synthesis of MsOTMS, MsOSiMe2Ph and TsOTMS was
performed in a similar manner to the preparation of trialkylsilyl esters of triflic acid
[24]. TfOTMS was obtained from Aldrich and used as provided. Nuclear Magnetic
1
Resonance spectroscopy was performed on a Brucker Avance-400. The H NMR
13
spectra were recorded at 400 MHz and C NMR spectra at 100 MHz in CDCl3. The
chemical shifts are reported in ppm relative to tetramethylsilane (TMS) as the internal
standard. The numbering of atoms in the 13С- and 1H-NMR spectra of the compounds
1b, 1d, 2a, 2b, 3b, 3c, 4a, 4b and 5. is shown in Figure 1. Elemental analysis was
performed using a Carlo-Erba CHN 1106 elemental analyser. Mass spectra were
obtained on a Finnigan 4021 instrument. The yields were calculated from the isolated
amount of alkenylsilanes obtained from starting alkynes.
4.2. The silylation of β,β−disubstituted 1-alkenylaluminums with silyl esters of
sulfonic acids.
4.2.1. Synthesis of trimethyl[(E)-2-methyl-1-octenyl]silane (1a) [22].
To a 25-mL, argon-swept flask, equipped with a magnetic stirrer and rubber septa,
was added 0.58 g (2 mmol) of Cp2ZrCl2 suspended in 5 mL of CH2Cl2 and 0.38 mL (4
mmol) of Me3Al (caution: organoaluminums are pyrophoric and can ignite on contact
with air, water or any oxidizer) at room temperature. All of the Cp2ZrCl2 dissolved to
give a lemon-yellow solution. To the solution was added 0.30 mL (0.22 g, 2 mmol) of
1-octyne at room temperature and stirred for 3 h. Trimethylsilyl methanesulfonate
(2.02 g, 12 mmol) was added to the reaction mixture and stirred at room temperature
for 18 hours. Then, the reaction mixture was diluted with 5 mL of hexane and 3 mL of
H2O was added dropwise while cooling the reactor flask in an ice bath. The
precipitate was filtered on a filter paper. The aqueous layer was extracted with diethyl
ether (3×5 mL). The combined organic layers were washed with brine (10 mL), dried
over anhydrous CaCl2 and concentrated in vacuo to give crude product as a colorless
oil. The residue was distilled through a micro column at 5 mmHg to give 1a (0.33 g,
о
о
82%) as a colourless oil. b.p. 80 – 82 С (5 mmHg) (lit. [22] b.p. 101-103 C (10
mmHg)). The spectral properties (1H NMR, C NMR, MS) were in good agreement
13
with those reported in the literature [22].
4.2.2. Synthesis of trimethyl[(E)-2-methyl-1-decenyl]silane (1b).
Using the procedure described above 0.28 g of 1-decyne (2 mmol) gave crude product
that was purified by flash chromatography (silica gel, n-hexane) to afford 1b (0.42 g,
1
93%) as a colourless oil. Rf(hexane) 0.81. H NMR (δ, ppm, J/Hz ): 0.12 (s, 9Н,

5
ACCEPTED MANUSCRIPT
С(12,13,14)Н3), 0.91 (t, 3Н, С(10)Н3, J = 6.8), 1.20-1.50 (m, 12Н, С(4-9)Н2), 1.79 (s,
3Н, С(11)Н3), 2.07 (t, 2Н, С(3)Н2, J = 7.2), 5.20 (s, 1H, C(1)H1). 13C NMR (δ, ppm):
0.11 (C(12,13,14 ), 14.11 (C(10)), 21.55 (С(11)), 22.68 (C(9)), 27.88, 29.29, 29.32,
29.52, 31.90 (C(4,5,6,7,8)), 42.68 (С(3)), 122.61 (C(1)), 155.73 (С(2)). MS (m/z, %):
226 (1) [M+], 211 (6) [М-Ме]+, 184 (1), 169 (1), 128 (31), 73 (100) [Ме3Si]+. Anal.
calcd for С14Н30Si, %: C, 74.25; Н, 13.35. Found, %: C, 74.64; Н, 13.21.
4.2.3. Synthesis of trimethyl[(E)-2-phenyl-1-propenyl]silane (1с) [25].
Using the procedure described above 0.20 g of ethynylbenzene (2 mmol) gave crude
product that was distilled through a micro column at 3 mmHg to afford 1c (0.34 g,
88%) as a colourless oil. b.p. 78 – 80 оС (3 mmHg). The spectral properties (1H NMR,
13C NMR) were in good agreement with those reported in the literature [25]. MS (m/z,
%): 190 (14) [M]+, 175 (61) [M-Me]+, 159 (16), 135 (100), 115 (12), 73 (21)
[Ме3Si]+.
4.2.4. Synthesis of dimethyl[(Z)-2-methyl-1-octenyl]phenylsilane (1d).
Using the procedure described above 0.22 g of 1-octyne (2 mmol) and 2.76 g of
dimethyl(phenyl)silyl methanesulfonate (12 mmol) instead of trimethylsilyl
methanesulfonate gave crude product that was purified by flash chromatography
(silica gel, n-hexane) to afford 1d (0.45 g, 86%) as a colourless oil. Rf(hexane) 0.8. 1H
NMR (δ, ppm, J/Hz ): 0.37 (s, 6Н, С(10,11)Н3), 0.92 (t, 3Н, С(8)Н3, J = 7.2), 1.20-
1.55 (m, 8H, C(4-7)H2), 1.72 (s, 3H, С(9)H3), 2.13 (t, 2Н, С(3)Н2, J = 8), 5.37 (s, 1H,
С(1)H1), 7.25-7.65 (m, 5H, Ph). 13C NMR (δ, ppm): -0.82 (C(10,11), 14.10 (C(8)),
22.05 (С(9)), 22.65, 27.87, 28.98, 31.78 (4C, C(4,5,6,7)), 42.76 (C(3)), 120.32 (C(1)),
127.68 and 133.76 (4С, С(13,14,16,17)), 128.59 (С(15)), 140.35 (С(12)), 157.81
(С(2)). MS (m/z, %): 260 (1) [M+], 245 (10) [М-Ме]+, 218 (1), 190 (13), 159 (7), 148
(26), 135 (100) [Ме2PhSi]+, 121 (36) [МеPhSi]+. Anal. calcd for С17Н28Si, %: C,
78.38; Н, 10.83. Found, %: C, 78.92; Н, 9.48.
4.3. The silylation of β−disubstituted 1-alkenylaluminums with trimethylsilyl
methanesulfonate.
4.3.1. Synthesis of trimethyl[(E)-1-octenyl]silane (2a) [26].
To 5 mL of hexane was added under an atmosphere of argon 0.22 g of 1-octyne (2
mmol) and 0.3 mL of DIBAL-H (2 mmol) and stirred for 5 hours at 50 oC. Then to the
reaction mixture was added 0.34 g of trimethylsilyl methanesulfonate (2 mmol) and
stirred for 18 hours at room temperature. The reaction mixture was diluted with 5 mL
of hexane and 3 mL of H2O was added dropwise while cooling the reactor flask in an
ice bath. The precipitate was filtered on a filter paper. The aqueous layer was
extracted with diethyl ether (3×5 mL). The combined organic layers were washed
with brine (10 mL), dried over anhydrous CaCl2 and concentrated in vacuo to give
crude product as a colorless oil. The residue was distilled through a micro column at 5
о
1
mmHg to give 2a (0.32 g, 88%) as a colourless oil. b.p. 67 – 69 С (5 mmHg). H
NMR (δ, ppm, J/Hz ): 0.07 (s, 9Н, С(9,10,11)Н3), 0.91 (t, 3Н, С(8)Н3, J = 6.8), 1.25-
1.63 (m, 8Н, С(4-7)Н2), 2.05-2.20 (m, 2Н, С(3)Н2), 5.66 (d, 1Н, С(1)Н1, J = 18.4),
6.00-6.10 (m, 1Н, С(2)Н1). 13C NMR (δ, ppm): 1.16 (C(9,10,11), 14.07 (C(8)), 22.61

6
ACCEPTED MANUSCRIPT
(С(7)), 28.67, 28.87, 31.74 (C(4,5,6)), 36.75 (С(3)), 129.45 (C(1)), 147.43 (С(2)). MS
(m/z, %): 184 (<1) [M+], 169 (77) [М-Ме]+, 114 (27), 109 (21), 99 (24), 73 (90)
[Ме3Si]+, 59 (100).
4.3.2. Synthesis of trimethyl[(E)-1-decenyl]silane (2b) [26].
Using the procedure described above 0.28 g of 1-decyne (2 mmol) gave crude product
that was distilled through a micro column at 5 mmHg to afford 2b (0.34 g, 81%) as a
о
1
colourless oil. b.p. 94 – 96 С (5 mmHg). H NMR (δ, ppm, J/Hz ): 0.07 (s, 9Н,
С(11,12,13)Н3), 0.91 (t, 3Н, С(10)Н3, J = 7.2), 1.20-1.45 (m, 12Н, С(4-9)Н2), 2.05-
2.15 (m, 2Н, С(3)Н2), 5.66 (d, 1Н, С(1)Н1, J = 18.8), 6.00-6.10 (m, 1Н, С(2)Н1). 13C
NMR (δ, ppm): 1.15 (C(11,12,13 ), 14.11 (C(10)), 22.68 (С(9)), 28.71 (С(8)), 29.21,
29.28, 29.48 (C(5,6,7)), 31.90 (С(4)), 36.76 (С(3)), 129.44 (C(1)), 147.44 (С(2)). MS
(m/z, %): 212 (2) [M+], 197 (76) [М-Ме]+, 181 (1), 114 (32), 99 (25), 85 (12), 73
(100) [Ме3Si]+.
4.4. The silylation of 2,3-dialkyl substituted aluminacyclopent-2-enes with silyl esters
of sulfonic acids.
4.4.1. Synthesis of (E)-3-propyl-3-heptenyl](trimethyl)silane (3a) [27].
To 0.058 g (0.2 mmol) of Cp2ZrCl2 suspended in 5 mL of hexane was added under an
atmosphere of argon 0.22 g of 4-octyne (2 mmol) and 0.3 mL of Et3Al (2 mmol) at 40
oC. After 2 h, to the reaction mixture was added 1.01 g of trimethylsilyl
o
methanesulfonate (6 mmol) at 40 C and stirred for 18 hours at room temperature.
Then, the reaction mixture was diluted with 5 mL of hexane and 3 mL of H2O was
added dropwise while cooling the reactor flask in an ice bath. The precipitate was
filtered on a filter paper. The aqueous layer was extracted with diethyl ether (3×5
mL). The combined organic layers were washed with brine (10 mL), dried over
anhydrous CaCl2 and concentrated in vacuo to give crude product as a colorless oil.
The residue was distilled through a micro column at 4 mmHg to give 3a (0.36 g, 84%)
о
13
as a colourless oil. b.p. 89 – 91 С (4 mmHg). The spectral properties (1H NMR, C
NMR) were in good agreement with those reported in the literature [27]. MS (m/z, %):
212 (4) [M+], 197 (1) [М-Ме]+, 169 (6) [М-Pr]+, 138 (2), 127 (2), 73 (100) [Ме3Si]+,
59 (8).
4.4.2. Synthesis of (E)-(3-butyl(4-2H1)oct-3-enyl)trimethylsilane (3b).
Using the procedure described above 0.28 g of 5-decyne (2 mmol) and 3 mL of D2O
instead of 3 mL of H2O gave crude product that was purified by flash chromatography
(silica gel, n-hexane) to afford 3b (0.42 g, 86%) as a colourless oil. Rf(hexane) 0.8. 1H
NMR (δ, ppm, J/Hz ): 0.01 (s, 9Н, С(13,14,15)Н3), 0.05-0.75 (m, 2Н, С(12)Н2), 0.85-
1.00 (m, 6Н, С(1,10)Н3), 1.25-1.45 (m, 8Н, С(2,3,8,9)Н2), 1.95-2.15 (m, 6Н,
С(4,7,11)Н2). 13C NMR (δ, ppm, J/Hz): -1.72 (C(13,14,15), 14.00 (C(1,10)), 15.11
(С(12)), 22.90 and 22.49 (C(2,9)), 27.29 and 29.62 (C(4,7)), 30.78 (С(11)), 31.37 and
1
32.40 (С(3,8)), 122.96 (C(6), t, JCD = 22), 141.74 (С(5)). Anal. calcd for С15Н31DSi,
%: C, 74.60. Found, %: C, 74.01.
4.4.3. Synthesis of [(Е)-3-Butyloct-3-enyl](dimethyl)phenylsilane (3c).

7
ACCEPTED MANUSCRIPT
Using the procedure described above 0.28 g of 5-decyne (2 mmol) and 1.38 g of
dimethyl(phenyl)silyl methanesulfonate (6 mmol) instead of trimethylsilyl
methanesulfonate gave crude product that was purified by flash chromatography
(silica gel, n-hexane) to afford 3c (0.54 g, 89%) as a colourless oil. Rf(hexane) 0.84.
1H NMR (δ, ppm, J/Hz ): 0.32 (s, 6Н, С(13,14)Н3), 0.80-1.05 (m, 6Н, С(12,8)Н3),
1.25-1.40 (m, 10Н, С(1,6,7,10,11)Н2), 1.95-2.10 (m, 6Н, С(2,5,9)Н2), 5.16 (t, 1Н,
С(4)Н1, J = 8), 7.35-7.60 (m, 5Н, Ph). 13C NMR (δ, ppm): -3.01 (C(13,14), 14.04
(C(8,12)), 14.11 (С(1)), 22.51 and 22.86 (C(7,11)), 27.45, 29.69, 30.79, 30.83, 32.40
(C(2,5,6,9,10)), 123.56 (С(18)), 127.71 and 133.60 (С(16,20,17,19)), 128.78 (C(4)),
139.56 (С(15)), 141.60 (С(3)). MS (m/z, %): 302 (1) [M+], 287 (1) [М-Ме]+, 274 (1)
[М-Et]+, 245 (1), 224 (11), 209 (5), 182 (4), 135 (100) [Ме2PhSi]+, 121 (8)
[МеPhSi]+. Anal. calcd for С20Н34Si, %: C, 79.39; Н, 11.33. Found, %: C, 79.87; Н,
12.48.
4.5. The silylation of aluminacyclopentanes with trimethylsilyl methanesulfonate.
4.5.1. Synthesis of trimethyl(3-[(2H1)methyl]nonyl)silane (4a).
To 0.058 g (0.2 mmol) of Cp2ZrCl2 suspended in 5 mL of hexane was added under an
atmosphere of argon 0.22 g of 1-octene (2 mmol) and 0.3 mL of Et3Al (2 mmol) at 40
oC. After 2 h, to the reaction mixture was added 1.01 g of trimethylsilyl
o
methanesulfonate (6 mmol) at 40 C and stirred for 18 hours at room temperature.
Then, the reaction mixture was diluted with 5 mL of hexane and 3 mL of D2O was
added dropwise while cooling the reactor flask in an ice bath. The precipitate was
filtered on a filter paper. The aqueous layer was extracted with diethyl ether (3×5
mL). The combined organic layers were washed with brine (10 mL), dried over
anhydrous CaCl2 and concentrated in vacuo to give crude product as a colorless oil.
The residue was distilled through a micro column at 5 mmHg to give 4a (0.34 g, 80%)
о
as a colourless oil. b.p. 93 – 95 С (5 mmHg). 1H NMR (δ, ppm, J/Hz ): 0.00 (s, 9Н,
С(11,12,13)Н3), 0.39-0.58 (m, 2Н, С(10)Н2), 0.86 (d, C(8)H2D, J = 4.4), 0.92 (t, 3Н,
С(1)Н3, J = 6.8), 1.00-1.40 (m, 13Н, С(2,3,4,5,6,7,9)Н2). 13C NMR (δ, ppm , J/Hz): -
1.75 (C(11,12,13), 13.45 and 14.10 (C(1,10)), 18.94 (C(8), t, 1JCD = 19), 22.71 (С(2)),
27.12, 29.75, 30.87, 31.98 (C(3,4,5,9)), 35.51 (С(6)), 36.49 (C(7)). MS (m/z, %): 215
(1) [M+], 200 (10) [М-Ме]+, 101 (18), 73 (100) [Ме3Si]+. Anal. calcd for С13Н29DSi,
%: C, 72.47. Found, %: C, 72.88.
4.5.2. Synthesis of trimethyl(3-phenylbutyl)silane (4b).
Using the procedure described above 0.21 g of styrene (2 mmol) and 3 mL of H2O
instead of 3 mL of D2O gave crude product that was distilled through a micro column
at 5 mmHg to afford 4b (0.32 g, 77%) as a colourless oil. b.p. 98 – 100 оС (5 mmHg).
1H NMR (δ, ppm, J/Hz ): 0.01 (s, 9H, С(11,12,13)Н3), 0.15-0.20 (m, 2Н, С(1)Н2),
1.27 (d, 3Н, С(4)Н3, J = 6.8), 1.5-1.65 (m, 2Н, С(2)Н2), 2.60-2.70 (m, 1Н, С(3)Н1),
7.10-7.50 (m, 5Н, Ph). 13C NMR (δ, ppm):1.72 (C(11,12,13), 14.67 (C(1)), 21.79
(С(4)), 32.63 (C(2)), 43.12 (C(3)), 125.75 (C(8)), 127.13 и 128.25 (4C, С(6,7,9,10)),
143.60 (С(5)).
MS (m/z, %): 206(<1) [M+], 191 (<1) [М-Ме]+, 178 (10) [М-Et]+.
Anal. calcd for С13Н22Si, %: C, 75.65; Н, 10.74; Si, 13.61. Found, %: C, 75.79; Н,
11.09.

8
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4.5.3. Synthesis of 2-[2-(trimethylsilyl)ethyl]-1-octanol (5).
To 0.058 g (0.2 mmol) of Cp2ZrCl2 suspended in 5 mL of hexane was added under an
atmosphere of argon 0.22 g of 1-octene (2 mmol) and 0.3 mL of Et3Al (2 mmol) at 40
oC. After 2 h, to the reaction mixture was added 1.01 g of trimethylsilyl
methanesulfonate (6 mmol) at 40 oC and stirred for 18 hours at room temperature. The
resultant mixture was cooled to 0°C and a dry oxygen was passed through for 2 h.
Then, the reaction mixture was diluted with 5 mL of hexane and 3 mL of 1N HCl was
added. The aqueous layer was extracted with diethyl ether (3×5 mL). The combined
organic layers were washed with brine (10 mL) and dried over anhydrous CaCl2.
Evaporation of solvent and purification of the residue by column chromatography
(EtOAc/ hexane=l:4 as eluant) gave 5 (0.39 g, 85%) as colorless oil.
1
Rf(EtOAc/hexane= l:5) 0.32. H NMR (δ, ppm, J/Hz ): 0.02 (s, 9Н, С(11,12,13)Н3),
0.46 (t, 2H, C(10)H2, J = 8.4), 0.88 (t, 3Н, С(1)Н3, J = 6.8), 1.20-1.45 (m, 13Н,
С(2,3,4,5,6,9)Н2, С(7)Н), 2.04 (br.s, OH), 3.54 (d, 2H, C(8)H2, J = 5.2). 13C NMR (δ,
ppm): -1.82 (C(11,12,13), 12.96 and 14.06 (C(1,10)), 22.65 (С(2)), 24.58 & 26.81 &
29.75 & 30.30 & 31.86 (C(3,4,5,6,9)), 43.12 (С(7)), 65.13 (C(8)). MS (m/z, %): 212
(4) [M-H2O] +, 169 (6), 73 (100) [Ме3Si]+, 59 (8). Anal. calcd for С13Н30ОSi, %: C,
67.75; Н, 13.12. Found, %: C, 67.81; Н, 12.99.
4.6. The preparation of trimethyl[(E)-2-methyl-1-octenyl]silane (1a) with the use of
TMSCl and TsONa.
a) To a 25-mL, argon-swept flask, equipped with a magnetic stirrer and rubber septa,
was added 0.58 g of Cp2ZrCl2 (2 mmol) suspended in 5 mL of CH2Cl2 and 0.38 mL of
Me3Al (4 mmol) (caution: organoaluminums are pyrophoric and can ignite on contact
with air, water or any oxidizer) at room temperature. All of the Cp2ZrCl2 dissolved to
give a lemon-yellow solution. To the solution was added 0.30 mL of 1-octyne (2
mmol) at room temperature and stirred for 3 h.
b) To a 25-mL, argon-swept flask, equipped with a magnetic stirrer, rubber septa and
reflux condenser, was added at room temperature 10 mL of dry toluene, 1.52 mL of
Me3SiCl (12 mmol) and 2.35 g of anhydrous TsONa (12 mmol). The reaction mixture
was refluxed for 10 minutes and then cooled to room temperature.
The reaction mixture (a) was added via syringe through rubber septa to the reaction
o
mixture (b) at 0 C and stirred at room temperature for 18 hours. Then, the reaction
mixture was diluted with 5 mL of hexane and 3 mL of H2O was added dropwise while
cooling the reactor flask in an ice bath. The precipitate was filtered on a filter paper.
The aqueous layer was extracted with diethyl ether (3×5 mL). The combined organic
layers were washed with brine (10 mL), dried over anhydrous CaCl2 and concentrated
in vacuo to give crude product as a colorless oil. The distillation of residue through a
micro column at 5 mmHg gave 1a (0.31 g, 79 %) as colorless oil.
Acknowledgments
This work was supported by Department of Chemistry and Material Sciences of the
Russian Academy of Sciences (program No.1 - OKhNM), which is gratefully
acknowledged.

9
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References and Notes
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[10] W.S. Park, W.R. Beard, inventors; Ethyl Corp., assignee. Process for
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[11] U.M. Dzhemilev, A.G. Ibragimov, R.R. Gilyazev, L.O. Khafizova, Zirconium-
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[13] D.E. Horn, E. Negishi, Selective carbon-carbon bond formation via transition
metal catalysts. 8. Controlled carbometalation. Reaction of acetylenes with

10
ACCEPTED MANUSCRIPT
organoalane-zirconocene dichloride complexes as a route to stereo- and regio-
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Dzhemilev, Regio- and stereoselective hydroalumination of disubstituted
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6222.

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O
S
(6 eq)
R''
R'Me2SiO
Me3Al (2 eq)
Сp2ZrCl2 (1 eq)
R
H
R
H
O
R
H
rt, 18h
Me
AlMe2
CH2Cl2, rt, 3h
Me
SiMe2R'
1a: R= n-C6H13; R'=Me;
R''=Me (82 %); Me3SiO (80 %);
n-Tol (85 %), Ph (86 %), CF3 (94 %)
1b: R= n-C8H17; R'=Me; R''=Me (93 %)
1c: R= Ph; R'=Me; R''=Me (88 %)
1d: R= n-C6H13; R'=Ph; R''=Me (86 %)
Scheme 1. The reaction of β,β-disubstituted 1-alkenylaluminums with silyl esters of
sulfonic acids.
DIBAL-H (1 eq)
hexane, 50 oC, 5h
R
H
H
R
H
H
MsOTMS (1 eq)
rt, 18h
R
H
Al(i-Bu)2
SiMe3
2a: R= n-C6H13 (88 %);
2b: R= n-C8H17 (81 %)
Scheme 2. The reaction of β-substituted 1-alkenylaluminums with MsOTMS.
Et3Al (2 eq)
Cp2TiCl2 (0.05 eq)
Bu
H
Bu
MsOTMS (6 eq)
rt, 18h
the reaction does
not proceed
hexane, rt, 6h
AlEt2
Bu
Bu
Me3Al (2 eq.)
MsOTMS (6 eq)
rt, 18h
Bu
Bu
Cp2ZrCl2 (1 eq.)
the reaction does
not proceed
CH2Cl2, rt, 3h
Me
AlMe2
Scheme 3. α,β−Disubstituted 1-alkenylaluminums do not react with MsOTMS.

13
ACCEPTED MANUSCRIPT
O
(3 eq)
Me
R'Me2SiO
rt, 18h
S
1.
R
O
R
Et3Al (1 eq)
Cp2ZrCl2 (0.1 eq)
R
R
R
R'Me2Si
hexane, 40 oC, 2h
Al
Et
R
1 or 2 H
2. 1H2O or 2H2O
3a: R= n-C3H7; R'=Me (84 %);
3b: R= n-C4H9; R'=Me (86 %) (2H2O was used)
3с: R= n-C4H9; R'=Ph (89 %)
Scheme 4. The reaction of 2,3-disubstituted aluminacyclopent-2-enes with MsOTMS
and MsOSiMe2Ph.
R
4a: R= n-C6H13 (80 %);
4b: R= Ph (77 %)
Me3Si
2H
2H2O
R
R
Et3Al (1 eq)
MsOTMS (3 eq)
rt, 18 h
Cp2ZrCl2 (0.1 eq)
Me3Si
MsO(Et)Al
hexane, 40 oC, 2h
R
Al
Et
O2
R= n-Hex
Hex
Me3Si
HO
5 (85 %)
Scheme 5. The reaction of 3-substituted aluminacyclopentanes with MsOTMS.

14
ACCEPTED MANUSCRIPT
10
9
7
8
7
8
7
5
5
8
6
6
5
3
3
H
H
6
4
4
3
2
2
H
4
1
1
9
12
2
10
Si
H
Si
1
9
12 13
11
11
10
1b
1d
2a
Si
11
13
17
14
14
16 15
10
9
2
1
11
12
8
9
7
4
6
8
10
6
3
5
3
11
5
2
10
6
13
13
3
8
H
4
1
4
7
16
9
Si
12
15
5
2
Si
7
1
14
14
11
17
18
D
15
H
Si
20
13
2b
3b
3c
12
19
2
1
7
8
2
1
4
4
9
6
3
3
6
6
8
3
5
5
4
10
5
9
7
9
7
2
11
11
11
10
8
10
1
Si
Si
Si
12
12
12
D
HO
13
13
13
5
4a
4b
Figure 1. The numbering of atoms in the 13С- and 1H-NMR spectra of the compounds
1b, 1d, 2a, 2b, 3b, 3c, 4a, 4b and 5.

ACCEPTED MANUSCRIPT
Highlights
•
•
•
•
Silyl esters of sulfonic acids are efficient silylating agents for alkenylaluminums.
The reaction proceeds in mild conditions to give alkenylsilanes in high yield.
The reaction with aluminacycles takes place on the less hindered reaction center.
TMSCl-TsONa is convenient reagent for silylation of organoaluminums.