A new protocol for synthesis of bifunctional alkynyl[vinyl or (E)-alkenyl]substituted organosilicon compounds

Article abstract of DOI:10.1016/j.jorganchem.2010.09.006

A new efficient route for selective synthesis of various, novel alkynyl(vinyl)substituted silicon (6) and alkynyl[(E)-alkenyl]substituted silicon compounds (9) via silylative coupling of alkynes and their products catalyzed by ruthenium(+2) complexes is d

Full text of DOI:10.1016/j.jorganchem.2010.09.006

Journal of Organometallic Chemistry 696 (2011) 527e532
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A new protocol for synthesis of bifunctional alkynyl[vinyl or (E)-alkenyl]
substituted organosilicon compounds
*
Beata Dudziec, Monika Rzonsowska, Bogdan Marciniec
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
A new efficient route for selective synthesis of various, novel alkynyl(vinyl)substituted silicon (6) and
alkynyl[(E)-alkenyl]substituted silicon compounds (9) via silylative coupling of alkynes and their prod-
ucts catalyzed by ruthenium(þ2) complexes is described. The tandem procedure facilitates the formation
of 9 synthesized in a high yield and stereoselectivity by a sequential silylative coupling of terminal
alkynes with divinylsubstituted silicon compounds followed by silylative coupling reaction of 6 with
styrenes in the presence of ruthenium hydride complexes ([RuHCl(CO)(PR3)3ꢀn]; R ¼ Cy (n ¼ 1), i-Pr
(n ¼ 1), Ph (n ¼ 0)).
Received 25 June 2010
Received in revised form
13 August 2010
Accepted 1 September 2010
Available online 21 September 2010
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Homogeneous catalysis
CeH activation
Ruthenium complexes
Silicon
Alkynes
1. Introduction
number of reports on their synthesis. It is probably due to the
possible problems in the known methods of their synthesis, espe-
Alkynylsubstituted organosilicon compounds bearing a second
unsaturated functional group at silicon atom, e.g. vinyl substituent,
make a class of attractive starting materials for organometallic
synthesis [1]. Recently, vinyl and alkynyl groups have been shown
to be of particular interest in the contest of consecutive intermo-
lecular 1,2-hydroboration and intramolecular 1,1-organoboration of
alkynyl(vinyl)silanes leading to effective synthesis of 1-silacyclo-
hex-2-enes [1]. Ethynyl(vinyl)silanes have also been applied as
reagents in photoinitiated reaction with ethanethiol and its deriv-
atives indicating the possibility of either vinyl or ethynyl group to
be involved in the homolytic addition of alkanethiols [2]. Another
transition-metal mediated reaction where alkynyl(vinyl)silanes can
be used as reagents is carbonylative, intermolecular alkyneealkyne
coupling in the presence of dicobalt carbonyl(0) complex [3]. This is
cially when there are other functional groups involved in the
compound structure. The most frequently used route to obtain the
above mentioned compounds is a stoichiometric reaction between
chlorosilanes and organolithium compounds [1a]. There have been
no papers on catalytic path leading to synthesis of functionalized,
unsaturated alkynylsubstituted organosilicon compounds.
The transition-metal (TM)-catalyzed (M ¼ Ru, Rh, Ir, Co) trans-
metallation of olefins with vinylsubstituted metalloid (E ¼ Si, Ge, B)
compounds, which we have worked out in the last two decades,
proved a valuable synthetic tool in preparation of vinylsubstituted
organometalloid reagents as well as polymers [4]. This process
appeared to be a new effective catalytic activation of the CeH bond
of olefins and CeE bond of organometalloid compounds (generally
occurring in the presence of complexes containing initially or
generating in situ MeH and MeE bonds).
a
modification of the well-known PausoneKhand reaction
(coupling between alkyne and alkene). The alkyneealkyne car-
bonylative coupling reaction has rarely been investigated although
it gives cyclopentadienones, potentially important intermediates.
Despite numerous possible applications of alkynyl(vinyl)
substituted organosilicon compounds, there are still a limited
In search for new reactions in the chemistry of vinylsubstituted
metalloid (E ¼ Si, Ge, B) compounds, we turned to acetylenes and
recently reported on new type of transformation, i.e. a ruthenium
(complexes containing [Ru]eH and/or [Ru]eE bonds eE ¼ Si, Ge)
catalyzed silylativeand germylativecouplingofterminalalkynes with
vinylsubstituted siliconand germanium compounds(Scheme 1)[5,6].
The reactions are widely recognized as efficient catalytic acti-
vation of sp-CeH and ]CeE (E ¼ Si, Ge) bonds of a vinylmetalloid
with evolution of ethylene. The mechanism of these reactions
* Corresponding author. Tel.: þ48 61 8291 509; fax: þ48 61 8291 508.
E-mail address: bogdan.marciniec@amu.edu.pl (B. Marciniec).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.09.006

528
B. Dudziec et al. / Journal of Organometallic Chemistry 696 (2011) 527e532
[Ru]eH complex [5]. Preliminary reports on alkynyl(vinyl)disilicon
compounds formation via ruthenium catalyzed silylative coupling
of terminal alkynes with divinylsubstituted silicon compounds
have been published by our group [5a].
Recently, particularly interesting reports on the possibility of
application of one-pot and sequential reactions in the synthesis of
organic compounds have appeared. There are numerous papers
concerning synthetic methodologies based on sequential hydro-
silylation/Hiyama coupling [7], silylative coupling/Hiyama coupling
[8], Heck arylation/Hiyama coupling processes [9]. The unsaturated
organosilicon compounds act as precursors or/and intermediates
and have been used as various double bond equivalents in the
Scheme 1. Silylative/Germylative Coupling of terminal alkynes with divinylsubstituted
silicon and germanium compounds.
consecutive construction of unsaturated, often
p-conjugated
organic systems. These alternative synthetic paths are essentially
attractive in view of the economy of the processes, eliminating the
step of isolation and purification of intermediate products.
Scheme 2. Silylative Coupling of terminal alkynes with divinylsubstituted silicon
compounds.
We here disclose a direct synthesis of various unsaturated
bifunctional alkynylsubstituted silicon compounds (6, 9) mediated
by ruthenium(þ2) hydride complexes ([RuHCl(CO)(PR3)3ꢀn]; R ¼ Cy
(n ¼ 1) (1), i-Pr (n ¼ 1) (2), Ph (n ¼ 0) (3)). The 6 are obtained via
silylative coupling (SC) reaction of terminal alkynes (4) with
divinylsubstituted silicon compounds (5). With regard to the
involves the insertion of vinyleE into the [Ru]eH bond and
metalloid transfer to the metal with elimination of ethylene and
generation of the [Ru]eE complex. It is followed by the insertion of
b-
alkyne into the [Ru]eE bond and
b-hydrogen transfer to the
metal to eliminate the substituted alkynylsilane and recovery of the
Table 1a
Silylative coupling of 4 with divinyl-disiloxane and -disilazane (5)a.
Entry
4
5
[Ru]:[5]:[4]
Conversion of 4 (%)(Yield of 6 (%))b
Selectivity: (6):(7) (%)
1
2
10ꢀ2:2:1e
41
67
92:8
86:14
10ꢀ2:2:1f
3
4
5
6
7
8
10ꢀ2:2:1h
10ꢀ2:1:1
59
63
97
99
75
48
67:33
77:23
88:12
77:6d
84:16
86:14c
10ꢀ2:2:1
10ꢀ2:4:1
0.5 ꢁ 10ꢀ2:2:1
HC^CSiMe2Ph
10ꢀ2:2:1
9
10ꢀ2:3:1g
98 (83)
6a
85:15
10
11
2 ꢁ 10ꢀ2:3:1
2 ꢁ 10ꢀ2:3:1
78 (70)
99 (91)
6b
6c
91:10c
92:8c
HC^CC5H11
HC^CSiEt3
12
10ꢀ2:2.5:1
77
64:36c
13
14
10ꢀ2:3:1
87
54
95:5
2 ꢁ 10ꢀ2:2.5:1
69:31
15
16
HC^CC5H11
2 ꢁ 10ꢀ2:2.5:1
10ꢀ2:2:1
94
58
87:13
HC^CSiMe2Ph
85:15c
17
10ꢀ2:3:1g
99 (73)
6d
73:27
18
2 ꢁ 10ꢀ2:3:1
2 ꢁ 10ꢀ2:3:1
84 (62)
98 (67)
6e
6f
72:28
65:35
19
HC^CC5H11
a
Reaction conditions: Ar, open glass ampoules, catalyst 1, toluene [0.5 M], 120 ꢂC, 24 h.
Yield of isolated product.
accompanied by traces of divinylsilicon homocoupling products.
accompanied by divinylsilicon homocoupling products.
80 ꢂC.
100 ꢂC.
b
c
d
e
f
g
h
catalyst 2.
catalyst 3.

B. Dudziec et al. / Journal of Organometallic Chemistry 696 (2011) 527e532
529
possible functionalization of the vinyl group left in the molecule,
those compounds are used as hydrogen acceptors in thewell-known
silylative coupling with styrenes, representative of alkenes [10]. The
reaction leads to a new group of bifunctional organosilicon
compounds, i.e. alkynyl[(E)-alkenyl]substituted silicon compounds
(9), which were also obtained using another synthetic path based on
sequential reaction of SC of divinylsubstituted silicon compounds
with alkynes followed by silylative coupling of obtained product
with styrenes in the presence of ruthenium(þ2) catalysts.
collected in Table 1a and Table 1b. Conversion of substrates and
selectivity were determined using a GC method with an internal
standard. The results show that the best catalytic system contains
at least 1% of [RuHCl(CO)(PCy3)2] relative to the alkynyl compound
and the reduction of the catalyst amount to 0.5 mol% lowers the
alkyne conversion (entry 7). Temperature is also important and
should be maintained in the range 110e120 ꢂC (entry 1, 2). The
alkyne conversion depends also on the nature of the substituents
(steric and electronic aspects) attached to the silicon atom as well
as the alkyne moiety. In order to avoid the high plausible dimer-
ization of terminal alkyne [12], the twofold (or more) excess of
divinyl compound is used. However, the overflow of 5 favours (in
the condition employed) silylative homocoupling reaction, known
since the 1990s [4b], so the reagents ratio is pivotal and optimi-
zation needs to be done. To investigate the generality of this reac-
2. Results and discussion
Our recent reports on selective synthesis of substituted alky-
nylsilanes have revealed the possibility of formation of alkynyl
(vinyl)substituted organosilicon compounds with a divinylsub-
stituted silicon compound used as a source of hydrogen acceptor
[5a,6b]. There are few examples of asymmetrically substituted
divinylorganosilicon compounds, yielded as main products and
efficiently isolated from the reaction mixture [11].
Herein, we present the results of our synthetic studies of 6 and
their further functionalization. The products desired were obtained
via silylative coupling reaction of terminal alkynes (4) with various
divinylsubstituted organosilicon compounds (5) containing one or
two silicon atoms in the molecule in the presence of ruthenium
(þ2) hydride complexes: [RuHCl(CO)(PCy3)2] (1), {RuHCl(CO)[P(i-
Pr3)2]} (2) (Scheme 2).
tion
a series of divinyldisilicon compounds bearing various
substituents was subjected to similar reaction conditions. The
results show high effectiveness of (1) and its regioselectivity to
produce alkynyl(vinyl)substituted silicon and disilicon compounds
where the two atoms of silicon are separated either by heteroatom
(Table 1a) or by alkyl/aryl unit (Table 1b). Although the main
product is in all cases inherently accompanied with traces of the
dialkynylsubstituted disilicon compounds (7) they can be discarded
during isolation.
Given our optimized conditions, we investigated the scope of
this reaction with divinylsilicon bearing only one metalloid atom in
the particle. To obtain high alkyne conversions, a six fold excess of
methyldivinylphenylsilane was used. The results obtained are
The reactions were performed in an open system under a gentle
flow of argon at 110e120 ꢂC for 24e48 h. The results obtained are
Table 1b
Silylative coupling of 4 with divinylsubstituted disilicon compounds (5)a.
Entry
1
4
5
[Ru]:[5]:[4]
10ꢀ2:1.8:1
Conversion of 4(%)(Yield of 6 (%))b
Selectivity: (6):(7) (%)
HC^CSiEt3
92 (75)
6g
6h
85:15
2
HC^CSiMe2Ph
10ꢀ2:2:1
91 (84)
97:3
3
4
10ꢀ2:2:1d
10ꢀ2:3:1
99 (82)
85 (75)
6i
6j
85:15
83:17
5
6
1.5 ꢁ 10ꢀ2:3:1d
1.5 ꢁ 10ꢀ2:3:1
62 (53)
72 (66)
6k
6l
98:2
HC^CC5H11
HC^CSiEt3
95:5c
7
8
10ꢀ2:4:1
10ꢀ2:3:1
48
58
94:6
HC^CSiMe2Ph
85:15c
9
10ꢀ2:3:1d
99 (89)
6m
90:10c
10
11
10ꢀ2:3:1d
95 (82)
88 (68)
91 (74)
6n
6o
6p
92:8
2 ꢁ 10ꢀ2:3.5:1
2 ꢁ 10ꢀ2:3.5:1
78:21
89:11
12
HC^CC5H11
a
Reaction conditions: Ar, open glass ampoules, catalyst 1, toluene [0.5 M], 120 ꢂC, 24 h.
Yield of isolated product.
accompanied by traces of divinylsilicon homocoupling products.
catalyst 2.
b
c
d

530
B. Dudziec et al. / Journal of Organometallic Chemistry 696 (2011) 527e532
Table 2
Table 3
Silylative coupling of 4 with methylphenyldivinylsilane (5)a.
Silylative coupling of 6 with styrenes (8)a.
Entry
4
Conversion of
Selectivity:
(6):(7) (%)
Entry
6
R00
Conversion of 6 (%)
(Yield of 9 (%))b
4 (%)(Yield of 6 (%))b
1
2
3
HC^CSiEt3
50 (40)
100 (88)
46c
6q
6r
93:7
95:5
1
2
H
98 (95)
9a
9b
HC^CSi(i-Pr)3
HC^CGeEt3
Cl
99 (96)
100:0
3
H
99 (96)
9c
4
57 (48)
98 (90)
6s
6t
94:6
93:7
4
5
Cl
H
99 (97)
99 (96)
9d
9e
5
6
67c (60)
80c (73)
6u
97:3
94:6
6
H
99 (93)
9f
7
HC^CC5H11
6w
a
Reaction Conditions: Ar, open glass ampoules; catalyst 1; [1]:[5]:[4] ¼ 10ꢀ2:6:1;
7
8
Cl
H
99 (94)
98 (94)
9g
9h
toluene [0.5 M]; 120 ꢂC; 24 h.
b
Yield of isolated product.
c
[1]:[5]:[4] ¼ 2 ꢁ 10ꢀ2:6:1.
9
Cl
H
99 (95)
99 (95)
9i
9j
collected in Table 2. Also in this case, the high effectiveness of (1)
and its regioselectivity to produce alkynyl(vinyl)substituted silicon/
germanium compounds is noted. The divinylsilicon moiety is less
susceptible to undergo homocoupling (silylative) reaction so the
two or six fold excess of methyldivinylphenylsilane could have been
applied to increase the alkyne conversion.
Trans-silylation of vinylsubstituted silanes was proved to be an
excellent method for stereoselective synthesis of (E)-(alkenyl)
silanes [10]. This fact was employed to modify the tri- and tetra-
vinylsubstituted cyclosiloxanes, cyclosilazanes [13] and also mon-
oalkynylsubstituted di- and trivinylcyclosiloxanes and silazanes
[14]. We also tried to apply this technique to perform further
functionalization of the remaining vinyl group at the silicon atom in
both groups of isolated alkynyl(vinyl)substituted silicon and dis-
ilicon compounds (6) (Scheme 3).
10
11
Cl
98 (95)
9k
12
13
H
H
98 (90)
95 (90)
9l
9m
14
15
Cl
H
97 (90)
97 (95)
9n
9o
16
17
Cl
99 (95)
96 (94)
97 (93)
9p
9q
9r
Me
OMe
18
a
Reaction conditions: Ar, open glass ampoules; catalyst 1, 2 or 3; toluene [0.5 M],
90 ꢂC; 24 h; [catalyst]:[6]:[8] ¼ 10ꢀ2:1:3.
b
Yield of isolated product.
Scheme 3.
The first step of this sequential process was the synthesis of 6.
The reaction conditions corresponded to those found for 6, i.e.
ruthenium(þ2) hydride complex (1 or 2) at 1e2 mol% loading,
toluene as solvent, optimized excess of 5 and temperature 120 ꢂC.
The course of the reaction was followed by gas chromatography.
After 24 h, the solvent (and the possible unreacted substrates) was
gently evaporated under vacuum pump and the components for
the silylative coupling of 6 with styrenes (8) (catalyst (1, 2 or 3) at
least 1 mol% loading, toluene and styrene or 4-C8H7R00) were
introduced. The second step of the reaction was performed at
a lower temperature (80e90 ꢂC) for 24 h. In the specified reaction
conditions, the desired alkynyl[(E)-alkenyl]substituted silicon
compounds (9je9p) were obtained with perfect stereoselectivity
and very high yield (Table 4). All of the compounds were isolated on
the silica gel chromatographic column (hexane) and their
Selected compounds containing vinyl and substituted alkynyl
moiety in the structure were successfully used as substrates of
silylative coupling reaction with styrenes (8) in the presence of
ruthenium(þ2) hydride complex (1, 2 or 3) yielding novel alkynyl
[(E)-alkenyl]substituted silicon compounds (9). Respective results
of this reaction are presented in Table 3.
All of these products were isolated and characterized by 1H, 13
C
NMR spectroscopy. The coupling constants of protons at carbon
double bond atoms (JHeH ¼ 19 Hz) evidence the (E) geometry of the
sp2-hybridized carbonecarbon bonds. The 1H, 13C{1H} NMR and
HETCOR 1H{13C} spectra of the selected product i.e. 1-{[(cyclohexyl)
ethynyl]dimethylsilyl}-4-{[(E)-styryl]dimethylsilyl}benzene
are presented in Supporting Information (Figs. 1, 2 and 3).
(9e)
The results of the study prompted us to perform experiments
aiming at working out the sequential reaction system to achieve 9
without isolation of 6. The selected divinylsubstituted silicon
compounds were used as substrates in silylative coupling reaction
with 4 followed, without isolation, by silylative coupling with
styrenes (8), according to Scheme 4.
Scheme 4.

B. Dudziec et al. / Journal of Organometallic Chemistry 696 (2011) 527e532
531
13C dC ¼ 77.0 ppm for CDCl3) or external Si(CH3)4
(
29Si dSi ¼ 0.00
Table 4
Sequence of reactions involving consecutive silylative coupling of 4 with selected
divinylsubstituted silicon compounds and silylative coupling of these products
with 8a.
ppm). Coupling constants are reported in Hz. Gas phase analyses
were performed on Varian CP-3800 gas chromatography (GC)
apparatus equipped with a TCD detector and capillary column VF-
5ms (30 m ꢁ 0.53 mm). Mass spectra of the reagents and products
were obtained by GCeMS analysis (Varian Saturn 2100T, equipped
with a CP-SIL 6CB column (30 m ꢁ 0.25 mm) and an ion trap
detector). Elemental analyses were performed on Vario EL Ele-
mantar (Germany). Column chromatography was conducted with
silica gel 60 (70e230 mesh, Fluka), deactivated by hexamethyldisi-
lazane prior to use, when needed. Toluene was dried by distillation
from sodium, similarly hexane was distilled from calcium hydride
under argon. Tetrahydrofuran (THF) was distilled from sodium/
benzophenone under argon. All liquid substrates were also dried
and degassed by bulb-to-bulb distillation under argon prior to use.
All the reactions were carried out under argon dry atmosphere.
5
4
[catalyst]:[5]:[4]
R00
Total
Yield
(%)b
1
10ꢀ2:3:1
H
80
9j
2
3
10ꢀ2:3:1
Cl
H
82
85
9k
9l
HC^CC5H11
2 ꢁ 10ꢀ2:3:1c
4
10ꢀ2:3:1c
H
85
9m
5
6
10ꢀ2:3:1c
10ꢀ2:6:1
Cl
H
86
85
9n
9o
HC^CSi(i-Pr)3
4.2. Materials
7
10ꢀ2:6:1
Cl
86
9p
Thechemicals were obtainedfrom thefollowing sources:toluene,
decane, andhexane(Fluka),1,1,3,3-tetramethyl-1,3-divinyldisiloxane
(SigmaeAldrich), 1,1,3,3-tetramethyl-1,3-divinyldisilazane (Sigmae
Aldrich), 1,1,3,3-tetraethoxy-1,3-divinyldisiloxane (Gelest), 1,4-bis
(dimethylovinylsilyl)ethane (Gelest), 1,4-bis(dimethylovinylsilyl)
benzene (Gelest), ethynylcyclohexane (SigmaeAldrich), 1-heptyn
(SigmaeAldrich), 1-ethynylcyclohexanol (SigmaeAldrich), 3-
methyl-1-pentyn-3-ol (SigmaeAldrich), ethynyltriethylsilane (Gel-
est), ethynyldimethylphenylsilane (Gelest), 1 M THF solution of
vinylmagnesium bromide (SigmaeAldrich), styrene (Sigmae
Aldrich), 4-chlorostyrene (SigmaeAldrich), 4-methylstyrene (Sigmae
Aldrich), 4-methoxystyrene (SigmaeAldrich). 1-ethynyl-1-(trime-
thylsilyloxy)cyclohexane, and 3-methyl-3-(trimethylsilyloxy)pent-1-
yne were prepared according to the modified literature procedures
[18]. The ruthenium complex [RuHCl(CO)(PCy3)2] (1), {RuHCl(CO)[P(i-
Pr)3]2} (2), [RuHCl(CO)(PPh3)3] (3) were prepared according to the
literature procedure [19].
a
Reaction condition: Ar, open glass ampoules, toluene [0.5 M]; 1st step: 120 ꢂC,
24 h, catalyst 1; 2nd step: 90 ꢂC, 24 h, catalyst 1 or 2 or 3, [catalyst]:[6]:[8] ¼
10ꢀ2:1:3.
b
Yield of isolated product.
catalyst 2 in the 1st step.
c
spectroscopic characteristics correspond with the analysis of 9
obtained according to the Scheme 3.
In order to verify the possibility of performing the total
synthesis of 9 based on a one-pot procedure we accomplished
relevant tests. However, after the 1st step of this process, in the
reaction mixture there were always residues of unreacted 5 which
was used in excess along with the product (6) and the rest of
catalyst (which most of decomposes after the reaction). In conse-
quence, the addition of catalyst and styrenes (8) to the reaction
bulb to complete the 2nd step of the synthesis of 9 resulted
a mixture of 9 and a product of silylative coupling of 5 with styrenes
(reaction known from the literature [15]). In order to avoid silyla-
tive coupling of unreacted 5 with styrenes used in the 2nd step of
the process, the remains of 5 needed to be evaporated (along with
the solvent), leaving the crude product (6) and decomposed cata-
lyst. Hence, to obtain 9 with very good conversion and selectivity
the sequential procedure is the most promising.
4.3. Catalytic examinations of silylative coupling reaction of
terminal alkynes (4) with divinylsubstituted organosilicon
compounds (5)
In a typical experiment, the ruthenium catalyst (1 or 2 mol%) was
placed in a glass ampoule under argon and dissolved in toluene. The
decane (5% by volume of all components), divinylsubstituted orga-
nosilicon compound and the acetylene (usually used in the molar
ratio: [Ru]:[5]:[4] ¼ (0.01e0.02) : (1.8e6) : 1) were added. Subse-
quently, the ampoule was heated to 120 ꢂC and maintained at that
temperature for 24 h. The progress of the reaction was monitored by
GC and GCeMS. The final products were separated from the residues
of the catalyst and reactants by purification on an SiO2 column
(modified with 15% of Et3N when needed) with hexane as eluent. All
the products (6) were colourless or pale yellow oily liquids.
3. Conclusion
In summary, we have devised a versatile protocol for preparation
alkynyl(vinyl)substituted silicon (6) and alkynyl[(E)-alkenyl]
substituted silicon compounds (9) from easily available terminal
alkynes, divinylsubstituted silicon compounds and styrenes [16]. The
synthetic methodology to obtain 9 involves a sequential silylative
coupling of terminal alkynes (4) with divinylsubstituted silicon
compounds (5) followed by silylative coupling reaction of 6 with
styrenes (8) in the presence of ruthenium(þ2) hydride complex [17].
The simplicity of the experimental technique and high yields of
resulting products enabled us to synthesize, isolate and characterized
38novelfunctionalizedalkynylsubstitutedorganosiliconcompounds.
4.4. Catalytic examinations of a sequential silylative coupling
reaction
In a typical catalytic test, alkynyl(vinyl)substituted organo-
silicon compound (6) was not isolated after silylative coupling
reaction with terminal alkynes (4) (5% decane as internal standard,
amount calculated from GC analyses). Then, the solvent and
possible remains of substrates were gently evaporated under
vacuum pump, leaving the crude product (6) and decomposed
catalyst. The ruthenium catalyst (1, 2 or 3) (1 mol%) was placed in
a glass ampoule. After that, appropriate amounts of toluene and
styrene were placed in the ampoule under argon afterwards
4. Experimental
4.1. General procedures
NMR spectra were recorded in CDCl3 using Varian Mercury (300
MHz) and Bruker Ultra Shield spectrometers (400 MHz) and refer-
enced to the residual protonated solvent peaks (1H dH ¼ 7.26 ppm,

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B. Dudziec et al. / Journal of Organometallic Chemistry 696 (2011) 527e532
[6] (a) B. Marciniec, B. Dudziec, K. Szubert, J. Walkowiak WO/2008/020774.
(b) B. Marciniec, H. qawicka, B. Dudziec, J. Organomet. Chem. 693 (2008)
235e240.
[7] B. Marciniec, H. Maciejewski, C. Pietraszuk, P. Pawluc, in: B. Marciniec (Ed.),
Hydrosilylation: A Comprehensive Review on Recent Advances, Springer,
2009, pp. 87e124 (Chapter 3 and references cited therein).
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(usually used at the molar ratio: [6]:[8] ¼ 1:3). Next, the mixture
was heated at 90 ꢂC and maintained at that temperature for 24 h.
The final products were separated using the analogous technique,
described above.
Acknowledgements
(b) W. Prukala, B. Marciniec, M. Majchrzak, M. Kubicki, Tetrahedron 63 (2007)
1107e1115;
(c) W. Prukala, M. Majchrzak, K. Posa1a, B. Marciniec, Synthesis (2008)
3047e3052.
Financial support from the Ministry of Science and Higher
Education (Poland) (Project No. N N204 265538) is gratefully
acknowledged.
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(b) T. Jeffery, B. Ferber, Tetrahedron Lett. 44 (2003) 193e197;
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Appendix. Supplementary material
[10] (a) B. Marciniec, C. Pietraszuk, Organometallics 16 (1997) 4320e4326;
(b) C. Pietraszuk, B. Marciniec, M. Jankowska, Pol. Pat., P-355875.
See Supplementary material for full 1H, 13C, and 29Si NMR
spectra, the GCeMS traces, and the elemental analysis data of the
products (6 and 9) as well as 1H, 13C{1H} NMR and HETCOR 1H{13C}
spectra of 9e (Figs. 1e3). Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/j.
biomaterials.2010.09.006.
ꢀ
(c) B. Marciniec, E. Walczuk-Gusciora, C. Pietraszuk, Organometallics 20
(2001) 3423e3428;
(d) B. Marciniec, I. Kownacki, M. Kubicki, Organometallics 21 (2002)
3263e3270;
(e) B. Marciniec, I. Kownacki, D. Chadyniak, Inorg. Chem. Commun. 2 (1999)
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