Efficient functionalisation of cubic monovinylsilsesquioxanes via cross-metathesis and silylative coupling with olefins in the presence of ruthenium complexes

Article abstract of DOI:10.1002/adsc.200900400

Monovinylheptaisobutylsilsesquioxane undergoes efficient cross-metathesis and silylative coupling with styrenes. Allyl derivatives were successfully tested in cross-metathesis in the presence of first generation Grubbs' catalyst, while heteroatom-substitu

Full text of DOI:10.1002/adsc.200900400

FULL PAPERS
DOI: 10.1002/adsc.200900400
Efficient Functionalisation of Cubic Monovinylsilsesquioxanes
via Cross-Metathesis and Silylative Coupling with Olefins in the
Presence of Ruthenium Complexes
a
a
a,
b
˙
Patrycja Zak, Cezary Pietraszuk, Bogdan Marciniec, * Grzegorz Spꢀlnik,
and Witold Danikiewiczb
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
a
´
Fax : (+48)-61-8291-508; phone: (+48)-61-8291-509; e-mail: bogdan.marciniec@amu.edu.pl
Institute of Organic Chemistry PAS, M. Kasprzaka 44/52, 01-224 Warsaw, Poland
b
Received: June 9, 2009; Published online: October 28, 2009
Abstract: Monovinylheptaisobutylsilsesquioxane un- nearly quantitative formation of E isomers. Only
dergoes efficient cross-metathesis and silylative cou- when vinyl ethers are used does the reaction lead to
pling with styrenes. Allyl derivatives were successful- a mixture of stereoisomers. Atmospheric pressure
ly tested in cross-metathesis in the presence of first photoACHTNUTRGNEiNUG onisation has been successfully used for re-
generation Grubbsꢁ catalyst, while heteroatom-sub- cording mass spectra of the functionalised silses-
stituted vinyl derivatives (vinyl ethers, 9-vinylcarb- quioxanes.
ACHTUNGTRENNUNGazole) efficiently undergo silylative coupling cata-
lysed by ruthenium hydride complexes. Both reac- Keywords: catalysis; metathesis; ruthenium com-
tions proceed highly stereoselectively and lead to plexes; silsesquioxanes; silylative coupling
Introduction
molecular and macromolecular compounds with vi-
nylsilicon functionality have been developed. Both
Polyhedral oligosilsesquioxanes of the general formu- methods, i.e., silylative coupling (Scheme 1) and
la (RSiO1.5)n constitute a class of organosilicon com- cross-metathesis (Scheme 2), are based on catalytic
pounds that currently have a strong impact on both transformations of vinylsilicon compounds with ole-
catalytic research and materials science.[1] A rapid fins and lead to the synthesis of the respective func-
growth in interest in the chemistry of polyhedral oli- tionalised vinylsilicon reagents.[2]
gosilsesquioxanes has been observed for the last two
Cross-metathesis proceeds via the carbene mecha-
decades, stimulated by the increasing number of nism and is catalysed by well-defined alkylidene com-
actual and postulated applications. Substituted cubic plexes of W, Mo or Ru.[3] In the presence of the first
silsesquioxanes containing a nanosized inorganic core generation Grubbsꢁ catalysts (1), second generation
(RSiO1.5)8, similar to the other octasilsesquioxanes, Grubbsꢁ catalyst and Hoveyda–Grubbsꢁ catalysts we
offer considerable potential for producing hybrid ma- have demonstrated the efficient cross-metathesis reac-
terials as the vertices of the cube can be easily func-
tionalised.[1] The vinyl group as substituent at the sil-
sesquioxane core (ViSiO1.5)8 is particularly interesting
for producing hybrid materials as it can be easily
functionalised by a variety of transformations.
In our group two universal, effective and syntheti-
cally attractive methods for the functionalisation of Scheme 2.
Scheme 1.
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tions of vinyltris(trimethylsiloxy)silane, vinyltrialkoxy-
In this paper, we report the synthesis of monovinyl-
silanes, trichloro- and generally electron-withdrawing substituted octasilsesquioxane and its efficient and
group-substituted vinylsilicon compounds with ole- stereoselective functionalisation via cross-metathesis
fins.[4] The reaction proceeds efficiently for a broad and silylative coupling with styrenes, vinyl- and allyl-
variety of vinylsilicon derivatives which do not bear a organic derivatives. Monofunctionalised octasilses-
methyl group at the vinylsilicon unit. Thus divinyldiar- quioxanes are commonly used as organic-inorganic
yldisiloxanes undergo cross-metathesis with styrenes hybrid monomers, e.g., building blocks for lumines-
and 1-decene,[5] while linear and cyclic vinylaryl-sub- cent model substances.[14]
stituted oligosiloxanes are efficiently functionalised
upon cross-metathesis with styrene, substituted styr-
enes, 1-alkene and selected allyl derivatives.[6]
Results and Discussion
Synthesis
Monovinylsilsesquioxane was synthesised via the hy-
drolytic condensation of incompletely condensed sil-
sesquioxane (i-Bu)7Si7O9(OH)3 (3) with vinyltrichlo-
AHCTUNGTREGrNNUN osilane (4) (Scheme 3). This synthetic methodology
is well-documented for the synthesis of monosubsti-
tuted silsesquioxane [1]. We applied the modified pro-
cedure described earlier[15] and were able to get an
The silylative coupling of olefins with vinylsilanes analytically pure sample with an isolated yield of 92%
proceeds according to a mechanism involving the acti- (see the Experimental Section).
À
À
vation of =C H and Si C= bonds (Scheme 1) and is
catalysed by complexes containing or generating hy-
dride ([M]-H) or silyl ([M]-Si) ligands (silicometallics) Functionalisation
(where M=Ru, Rh, Ir, Co).[7] A wide variety of vinyl-
substituted silanes,[2] cyclosiloxane trimers[8] and tet- Cross-Metathesis
ramers[9] and, recently, linear vinyl-substituted oligo-
and polysiloxanes[10] have been effectively functional- Treatment of the 1:1 mixture of monovinylheptaiso-
ised via silylative coupling with styrene and some butyl-substituted silsesquioxane and styrene in
other olefins in the presence of ruthenium hydride CH2Cl2 at 408C with 1 mol% of first generation
complexes,
e.g.,
[RuHCl(CO)
G
or Grubbsꢁ catalyst (1) gave rise to the slow evolution of
[RuHCl(CO)
N
ethene and formation of the substituted silsesquiox-
There is a limited number of reports on the applica- ane (Scheme 4).
tion of cross-metathesis for modification of vinyl-sub-
Monitoring of the reaction course by gas chroma-
stituted silsesquioxanes. In 1997 Feher reported the tography showed the gradual consumption of the sub-
functionalisation of cubic (ViSiO1.5)8 via cross-meta- strates. Application of a small (one and a half-fold)
thesis with selected olefins in the presence of excess of styrene resulted in complete conversion
Schrockꢁs catalyst.[11] A highly efficient cross-metathe- being observed after 6 h of the reaction. 1H NMR
sis of octavinylsilsesquioxanes with selected olefins in analysis of the reaction mixture revealed selective for-
the presence of Grubbsꢁ catalyst (1) has also been re- mation of the cross-metathesis product. The cross-
alised in our laboratory.[12] Moreover, we have demon- metathesis was highly stereoselective. The exclusive
strated the high activity of ruthenium hydride com- formation of E-isomers was observed for all olefins
plexes in the silylative coupling of vinyl-substituted tested (Scheme 4). A number of substituted styrenes
silsesquioxanes[12] and spherosilicates[13] with styrene were screened in the cross-metathesis with monovi-
and some other olefins.
nylheptaisobutyl-substituted silsesquioxane. In all
Scheme 3.
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Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross-Metathesis
FULL PAPERS
Scheme 4.
Scheme 5.
cases complete conversion was observed after 6 or
The high stereoselectivity of the cross-metathesis of
18 h of reaction in refluxing dichloromethane allylbenzene and allylsilanes with vinylsilanes agrees
(Table 1). In the reaction of 5 with 4-methyl-substitut- well with our previous observations.[4b] Moreover, ef-
ed styrene, a three-fold excess of styrene was used to forts have been made to perform the cross-metathesis
increase the reaction rate and ensure complete con- of 5 with vinylanthracene and vinylphthalimide. How-
version.
ever, under the conditions used (temperature up to
Allylbenzene and allyltrimethylsilane, exemplary 1108C and catalyst concentration up to 4 mol%) no
allyl-substituted olefins, undergo efficient and stereo- transformation was observed. The inactivity of the
1
selective cross-metathesis with 5. H NMR spectro- ruthenium carbene complex in reactions with these
scopic analysis of the post-reaction mixture demon- reagents is very likely caused by the formation of
strated the exclusive formation of E-isomers. Howev- stable alkylidene complexes: anthracenyl-substituted
er, in the reaction of 5 with allylbenzene, besides the ruthenium alkylidene and Fischer-type N-stabilized al-
expected product (7f), the formation of its isomer kylidene with intramolecular coordination of the car-
(8f) (yield 15%) was observed (Scheme 5). A similar bonyl group to ruthenium as it was postulated by
isomerization was not observed for the reaction with Grubbs for pyrrolidone.[16] Reactions of silsesquioxane
allyltrimethylsilane.
(5) with vinyl ethers have not been tested in the pres-
Table 1. Cross-metathesis and silylative coupling of monovinyloctasilsesquioxane (5) with olefins.
Olefin
Cross-metathesis[a]
Yield [%] (isolated)
Silylative coupling[b]
Yield[c] [%] (isolated)
[5]:[6] (time)
[5]:[6] (time)
6a
6b
6c
6d
6e
6f
6g
6h
6i
1:2 (6)
1:1.5 (6)
1:1.5 (6)
1:1.5 (6)
1:3 (6)
1:2 (18)
1:3 (18)
–
100 (97)
100 (97)
100 (95)
100 (96)
100 (94)
100 (87)[d]
85[e]
–
–
–
1:1.5 (6)
1:1.5 (6)
1:1.5 (6)
1:1.5 (6)
1:3 (6)
–
100 (95)
100 (95)
100 (95)
100 (92)
100 (94)
–
–
–
1:2 (18)
1:2 (18)
1:3 (24)
100 (88)[f,g]
100 (93)[f]
100 (85)[h]
–
–
6j
[a]
Cross-metathesis: CH2Cl2, reflux, argon, [RuCl2CAHTUNGTRENN(NUG PCy3)2ACHTUGNTRENNNUG
Silylative coupling: CH2Cl2, reflux, argon, [RuHCl(CO)
Isomer E if not otherwise indicated.
1 was used as catalyst (2 mol%).
15% of 8f was formed (see text).
Toluene, 808C, mixture of isomers formed E/Z=6/1.
Isolated sample contains 10 mol% of 5.
Toluene, 1108C, 2 was used as catalyst (4 mol%), closed high-pressure Schlenk flask.
(=CHPh)] (1 mol%).
A
[b]
[c]
[d]
[e]
[f]
[g]
[h]
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ence of a ruthenium alkylidene catalyst. It was dem- double bond and cis-trans isomerisation) leading to a
onstrated earlier that, under the conditions used, in- mixture of products. As the isomerisation cannot be
stead of metathesis, silylative coupling takes place, avoided, the silylative coupling of isomerising olefins
which is catalysed by ruthenium hydride complexes has no synthetic potential. The results of our catalytic
formed via thermal decomposition of ruthenium alk- examinations are summarized in Table 1. These re-
A
sults were obtained in the reaction conditions (cata-
lyst concentration, solvent, temperature and time) op-
timised on the basis of a number of catalytic experi-
ments.
Silylative Coupling
The mechanism explaining the effect of copper(I)
Heating of the 1:1.5 mixture of monovinylheptaisobu- chloride addition on the reaction course was not ex-
tyl-substituted silsesquioxane and styrene in CH2Cl2 amined. The reasonable explanation reported in the
at 408C with 1 mol% of (2) (in relation to a molar literature for similar systems indicates that copper salt
amount of vinylsilsesquioxane) and five-fold excess of acts as a phosphine scavenger and thus facilitates the
CuCl (in relation to a molar amount of catalyst) led formation of catalytically active species.[19]
to the evolution of ethene and formation of the sub-
stituted silsesquioxane (Scheme 6), similarly as ob-
1
served for cross-metathesis. H NMR analysis of the Labelling Studies
reaction mixture revealed the selective formation of
the functionalised silsesquioxane.
Present knowledge of the reactivity of the Grubbsꢁ
A number of styrenes were tested in the silylative type ruthenium catalyst indicates the possibility of in-
coupling reaction performed in the presence of a cata- terconvertions of alkylidene and hydride com-
lytic system consisting of [RuHCl(CO)ACTHNUTRGNEUNG
(PCy3)2] (2) plexes.[20] Therefore, in order to distinguish between
and copper(I) chloride.[18] A nearly quantitative for- the carbene mechanism (characteristic of olefin meta-
mation of functionalised silsesquioxane was observed thesis) and non-carbene mechanism (characteristic of
after 6 h of reaction in boiling CH2Cl2. Similarly to silylative coupling) operating in the presence of hy-
cross-metathesis, silylative coupling proceeds highly dride and silyl complexes,[2] the reaction of 5 with sty-
regio- and stereoselectively and results in the exclu- rene-d8 was performed in the presence of 1 and in a
sive formation of E-isomers. More forcing conditions separate experiment in the presence of 2.[7b] If the re-
(808C, toluene) and a two-fold excess of olefin were action followed the carbene mechanism, it should
required when vinyl alkyl ethers were tested as reac- result in formation of silylstyrene-d6 and ethylene-d2
tion partners. Under optimised conditions, complete (Scheme 7). In contrast, the insertion-elimination
conversions were observed after 18 h of the reaction. mechanism[7c] should afford the formation of silylstyr-
1
However, the H NMR spectrum of the reaction mix- ene-d7 and ethylene-d (Scheme 8), at least at the ini-
ture revealed the formation of a mixture of stereoiso- tial stage of the reaction.
mers (E/Z=6/1). An efficient transformation of 9-vi-
1H NMR spectroscopic analysis of the products
nylcarbazole was obtained by using relatively harsh formed in the reaction performed in the presence of 1
conditions (refluxing toluene, 4 mol% of 2). Such con-
ditions ensure the highly stereoselective formation of
carbazole-functionalised silsesquioxane 7j.
Silylative coupling of allyl derivatives in the pres-
ence of ruthenium hydride complexes is always ac-
companied by isomerisation (migration of the C=C
Scheme 7.
Scheme 6.
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Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross-Metathesis
FULL PAPERS
the M+· ion is also observed. Elemental analyses were per-
formed by the analytical laboratory of the Institute of Or-
ganic Chemistry PAS in Warsaw.
The chemicals were obtained from the following sources:
vinyltrichlorosilane, allyltrimethylsilane and vinyltrimethylsi-
lane from ABCR, styrene, 4-chlorostyrene, 4-methoxystyr-
ene, 4-bromostyrene, 4-methylstyrene, allylbenzene, tert-
butyl vinyl ether, butyl vinyl ether, 9-vinylcarbazole, di-
chloromethane, benzene-d6, decane, dodecane, copper(I)
chloride, anhydrous magnesium sulphate, calcium hydride
and first generation Grubbsꢁ catalyst from Aldrich, triethyl-
Scheme 8.
revealed the formation of silylstyrene-d6 accompanied
by small amount of silylstyrene-d0 as the product of
stoichiometric metathesis of monovinylsilsesquioxane
with benzylidene complex (1). On the other hand,
when the reaction was catalysed by 2, E-1-phenyl-2-
(silyl)ethene-d7 was produced. The results of experi-
ments with deuterium labelled styrene clearly demon-
strate that functionalisation of 5 actually can be per-
formed via two different mechanisms depending on
the catalyst used.
AHCTUNGTRENNUNG
pentane from Chempur. [RuHCl(CO)ACHTNUTRGNE(UNG PCy3)2] was prepared
according to the literature procedure.[22] All solvents were
dried prior to use over CaH2 and stored under argon.
CH2Cl2 was additionally passed through a column with alu-
mina and after that it was degassed by repeated freeze-
pump-thaw cycles. All syntheses and catalytic tests were car-
ried out under dry argon.
Conclusions
Synthesis of Monovinylheptaisobutylsilsesquioxane
Cubic monovinyl-substituted silsesquioxane under-
goes efficient functionalisation via cross-metathesis
and silylative coupling with styrenes and selected
vinyl and allyl derivatives in the presence of rutheni-
um complexes. Both reactions proceed highly stereo-
selectively for all olefins tested. Cross-metathesis and
silylative coupling are convenient and complementary
synthetic routes leading to the functionalisation of
vinyl-substituted silicon derivatives. It was found that
the best ionisation method for recording mass spectra
of silsesquioxanes was an atmospheric pressure photo-
ionisation (APPI) procedure with or without a
dopant, depending on the structure of the analysed
compound.
A two-necked, 500-mL flask equipped with reflux condenser
and connected to gas and vacuum line was charged under
argon with trisilanol (3) (3 g, 3.8ꢃ10À3 mol), pentane
(300 mL) and triethylamine (1.6 mL, 12.0 equiv.). The mix-
ture was cooled down in an ice bath to 08C and ViSiCl3
(0.52 mL, 4.0ꢃ10À3 mol) was quickly added in one portion,
which results in the formation of a white precipitate. The
suspension was stirred for 24 h at room temperature and fil-
tered on a glass frit. The precipitate was washed with pen-
tane (3ꢃ50 mL). The filtrate, reduced to 100 mL in volume,
was extracted three times with 30 mL of water to remove
residues of ammonium salt. The organic phase was dried
with MgSO4. Evaporation gave the analytically pure product
as a white powder; yield: 2.95 g (92%). 1H NMR (C6D6):
d=0.80–0.87 (m, 14H, CH2), 1.05–1.12 (m, 42H, CH3),
À
2.03–2,15 (m, 7H, CH), 5.97–6.26 (m, 3H, CH=CH2);
13C NMR (C6D6): d=22.9, 23.1 (CH2), 24.3, 24.4 (CH), 25.9,
26.0 (CH3), 130.3 (=CHSi), 136.4 (=CH2); 29Si NMR (C6D6):
d=À66.9, À67.4 (core), À80.9 (=CHSi); APPI-MS: m/z-
Experimental Section
AHCTUNGTRENNUNG
([M+H]+, % intensity)=843 (100), 844 (77), 845 (59), 846
General Methods and Chemicals
(30), 847 (14); anal. calcd. for: C30H66O12Si8 (%): C 42.72, H
7.89; found: C 42.61, H 8.16.
1H NMR and 13C NMR spectra were recorded in C6D6 on a
Varian Gemini 300 instrument at 300 and 75 MHz, respec-
tively. 29Si NMR spectra were recorded in C6D6 on a Varian
Avance 600 instrument at 119.203 MHz. Atmospheric pres-
sure photoionisation mass spectra (APPI-MS) were record-
ed on a 4000 Q Trap mass spectrometer (Applied Biosys-
tems) equipped with a PhotoSpray ion source. Compounds
with an aromatic substituent were dissolved in dichlorome-
thane (~1 mg in 5 mL) and diluted with methanol about ten
thousand times. Flow rate was 100 mLminÀ1, IS=1500 V,
source temperature=2008C and DP=20 V. No dopant was
used. Samples without aromatic substituents (5, 7g and 7i)
were dissolved and diluted as described above using hexane
instead of methanol. Flow rate was 100 mLminÀ1, IS=
1500 V, source temperature=3008C and DP=60 V. Toluene
was used as a dopant with a flow rate at 10 mLminÀ1. The
main signal in all spectra corresponds to the protonated
molecule (M+H+), however for compounds 7f, 7g and 7j
General Procedure for Catalytic Tests
Cross-metathesis: A 5-mL glass reactor equipped with reflux
condenser and connected to gas and vacuum line was
charged under argon with monovinylsilsesquioxane (5)
(0.05 g, 5.93ꢃ10À5 mol), CH2Cl2 (2 mL), decane or dodecane
(20 mL) and olefin (amounts depending on the olefin, see
details under Table 1). The mixture was warmed up to 458C
in an oil bath and first generation Grubbsꢁ catalyst
(0.0005 g, 5.93ꢃ10À7 mol) or (0.001 g, 1.19ꢃ10À6 mol)
(amounts depend on the olefin, see details under Table 1)
was added to the mixture under argon. The reaction mixture
was heated under reflux for 24 h. Conversion of the sub-
strate was monitored by gas chromatography. Reaction
1
yields were calculated on the basis of the H NMR spectra
of the reaction mixture.
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Silylative coupling: A 5-mL glass reactor equipped with
reflux condenser and connected to gas and vacuum line was
charged under argon with monovinylsilsesquioxane (5)
(0.05 g, 5.93ꢃ10À5 mol), CH2Cl2 (2 mL; or toluene for reac-
tion with vinyl ethers), decane or dodecane (20 mL) and
olefin (amount depends on the required silsesquioxane:ole-
fin molar ratio). The mixture was warmed up in an oil bath
to 458C (for reaction performed in with CH2Cl2) or 808C
(for the reaction performed in toluene) and [RuHCl(CO)-
of reaction copper(I) chloride (0.0023 g, 2.37 ꢃ10À5 mol)
was added. The reaction mixture was heated in the closed
vessel for 24 h. Then the solvent was evaporated under
vacuum and acetone (2 mL) was added to the remaining
contents to form a colourless precipitate. The precipitate
was filtered off, dissolved in hexane and purified by column
chromatography (silica gel 60/hexane) to remove ruthenium
complexes. Evaporation of the solvent gives the analytically
pure sample (white powder).
ACHTUNGTRENNUNG
(PCy3)2] (0.0004 g, 5.93ꢃ10À7 mol) was added. After 5 min
of the reaction copper(I) chloride (0.0003 g, 2.97ꢃ10À6 mol)
was added. The reaction mixture was heated for 24 h. Con-
version of the substrate was monitored by gas chromatogra-
phy. Reaction yields were calculated on the basis of the
1H NMR spectra of the reaction mixture.
Analytical Data of Isolated Products
1
7a: H NMR (C6D6): d=0.86–0.91 (m, 14H, CH2), 1.08–1.13
(m, 42H, CH3), 2.05–2.21 (m, 7H, CH), 6.47 (d, 1H, J=
19.2 Hz, =CHSi), 7.05–7.1 (m, 3H, Ph), 7.3–7.4 (m, 2H, Ph),
7.56 (d, 1H, J=19.2 Hz, =CHPh); 13C NMR (C6D6): d=
22.9, 23.1 (CH2), 24.3, 24.4 (CH), 25.9, 26.0 (CH3), 118.6
(=CHSi), 127.1, 128.9, 129.0 (C6H5), 137.8 (ipso-C of C6H5),
149.3 (=CHPh); 29Si NMR (C6D6): d=À66.9, À67.3 (core),
À79.0 (=CHSi); APPI-MS: m/z ([M+H]+, % intensity)=
919 (100), 920 (89), 921 (68), 922 (36), 923 (18), 924 (7);
anal. calcd. for C36H70O12Si8 (%): C 47.02, H 7.67; found: C
46.89, H 7.89; mp 157–1588C.
Synthesis of Functionalised Monovinylsilsesquioxanes
Via cross-metathesis with olefins (general procedure): A 5-
mL glass reactor equipped with reflux condenser and con-
nected to argon/vacuum line was charged under argon with
monovinylsilsesquioxane (0.1 g, 1.19ꢃ10À4 mol), CH2Cl2
(3 mL) and olefin (amounts depend on the required silses-
quioxane:olefin molar ratio). The mixture was warmed up
to 458C in an oil bath and first generation Grubbsꢁ catalyst
(0.001 g, 1.19ꢃ10À6 mol) or (0.002 g, 2.37ꢃ10À6 mol) was
added under argon. The reaction mixture was heated under
reflux for 24 h. Then the solvent was evaporated under
vacuum and cold acetone (2 mL) was added to remaining to
form a colourless precipitate. The precipitate was filtered
off, dissolved in hexane and purified by column chromatog-
raphy (silica gel 60/hexane) to remove ruthenium com-
plexes. Evaporation of the solvent gives an analytically pure
sample (white powder).
1
7b: H NMR (C6D6): d=0.87–0.92 (m, 14H, CH2), 1.09–
1.14 (m, 42H, CH3), 2.08–2.20 (m, 7H, CH), 3.23 (s, 3H,
OMe), 6.36 (d, 1H, J=19.2 Hz, =CHSi), 6.68 (d, 2H, J=
8.8 Hz, C6H4), 7.33 (d, 2H, J=8.8 Hz, C6H4), 7.56 (d, 1H,
J=19.2 Hz, =CHAr); 13C NMR (C6D6): d=23.0, 23.1 (CH2),
24.4, 24.5 (CH), 25.9, 26.0 (CH3), 54.7 (OMe), 114.4 (m-C of
C6H4OMe), 115.6 (=CHSi), 128.6 (o-C of C6H4OMe), 130.7
(ipso-C of C6H4OMe), 148.9 (=CHC6H4OMe), 160.8 (ipso-C
at OMe of C6H4OMe); 29Si NMR (C6D6): d=À66.91, À67.32
(core), À78.51 (=CHSi); APPI-MS: m/z ( [M+H]+, % in-
tensity)=949 (100), 950 (82), 951 (56), 952 (29), 953 (13);
anal. calcd. for C37H72O13Si8 (%): C 46.80, H 7.64; found: C
46.88, H 7.58; mp 183–1848C.
Via silylative coupling with olefins (general procedure): A
5-mL glass reactor equipped with reflux condenser and con-
nected to gas and vacuum line was charged under argon
with monovinylsilsesquioxane (0.1 g, 1.19ꢃ10À4 mol),
CH2Cl2 (or toluene for reaction with vinyl ethers, 3 mL) and
olefin (the amount depends on the required silsesquiox-
1
7c: H NMR (C6D6): d=0.87–0.91 (m, 14H, CH2), 1.08–
1.13 (m, 42H, CH3), 2.07–2.21 (m, 7H, CH), 6.32 (d, 1H,
J=19.2 Hz, =CHSi), 6.93 (d, J=8.2 Hz, 2H, C6H4Br), 7.16
(d, J=8.2 Hz, 2H, C6H4Br), 7.33 (d, 1H, J=19.2 Hz, <C=
>CHAr); 13C NMR (C6D6): d=22.9, 23.1 (CH2), 24.4, 24.5
(CH), 25.9, 26.0 (CH3), 119.6 (=CHSi), 123.2 (ipso-C at Br
of C6H4Br), 128.6 (o-C of C6H4Br), 132.05 (m-C of C6H4Br),
136.6 (ipso-C of C6H4Br), 147.8 (=CHAr); 29Si NMR (C6D6):
d=À66.86, À67.29 (core), À79.38 (=CHSi); APPI-MS: m/z
([M+H]+, % intensity)=997 (65), 998 (53), 999 (100), 1000
(72), 1001 (51), 1002 (23), 1003 (10); anal. calcd. for
C36H69BrO12Si8 (%): C 43.30, H 6.97; found: C 43.29, H
6.98; mp 200–2018C.
ACHTUNGTRENNUNGane:olefin molar ratio). The mixture was warmed up in an
oil bath to 458C (for reaction performed in with CH2Cl2) or
808C (for reaction performed in toluene) and [RuHCl(CO)-
ACHTUNGTRENNUNG
(PCy3)2] (0.0009 g, 1.19ꢃ10À6 mol) was added. After 5 min
of reaction copper(I) chloride (0.0006 g, 5.93ꢃ10À6 mol) was
added. The reaction mixture was heated for 24 h. Then the
solvent was evaporated under vacuum and acetone (2 mL)
was added to the remaining contents to form a colourless
precipitate. The precipitate was filtered off, dissolved in
hexane and purified by column chromatography (silica gel
60/hexane) to remove ruthenium complexes. Evaporation of
the solvent gives the analytically pure sample (white
powder).
1
7d: H NMR (C6D6): d=1.02–1.06 (m, 14H, CH2), 1.23–
1.28 (m, 42H, CH3), 2.20–2.35 (m, 7H, CH), 6.46 (d, 1H,
J=19.1 Hz, =CHSi), 7.30–7.33 (m, 4H, C6H4Cl), 7.50 (d,
1H, J=19.1 Hz, =CHAr); 13C NMR (C6D6): d=23.0, 23.1
(CH2), 24.4, 24.5 (CH), 25.9, 26.0 (CH3), 119.5 (=CHSi),
128.8 (o-C of C6H4Cl), 129.1 (m-C of C6H4Cl), 134.8 (ipso-C
at Cl of C6H4Cl), 136.2 (ipso-C of C6H4Cl), 147.7
(=CHC6H4Cl); 29Si NMR (C6D6): d=À66.86, À67.31 (core),
À79.38 (=CHSi); APPI-MS: m/z ([M+H]+, % intensity)=
953 (100), 954 (78), 955 (86), 956 (53), 957 (32), 958 (15),
959 (6); anal. calcd. for C36H69ClO12Si8 (%): C 45.32, H 7.29;
found: C 45.33, H 7.35; mp 192–1938C.
Silylative Coupling of Monovinylsilsesquioxane with
9-Vinylcarbazole
A 10-mL high-pressure Schlenk vessel connected to gas and
vacuum line was charged under argon with monovinylsilses-
quioxane (0.1 g, 1.19ꢃ10À4 mol), toluene (2 mL) and 9-vinyl-
carbazole (0.0688 g, 3.56ꢃ10À4 mol). The mixture was
warmed up in an oil bath to 1108C and [RuHCl(CO)-
ACHTUNGTRENNUNG
(PCy3)2] (0.0034 g, 4.74ꢃ10À6 mol) was added. After 5 min
2680
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ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2675 – 2682

Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross-Metathesis
FULL PAPERS
1
7e: H NMR (C6D6): d=0.86–0.92 (m, 14H, CH2), 1.08–
1.13 (m, 42H, CH3), 2.05 (s, 3H, C6H4-CH3) 2.06–2.21 (m,
7H, CH), 6.46 (d, 1H, J=19.2 Hz, =CHSi), 6.91 (d, 2H, J=
8.1 Hz, C6H4Me), 7.33 (d, 2H, J=8.1 Hz, C6H4Me), 7.59 (d,
1H, J=19.2 Hz, =CHC6H4Me); 13C NMR (C6D6): d=23.0,
23.1 (CH2), 24.4, 24.5 (CH), 25.9, 26.0 (CH3), 24.4
(C6H4CH3), 118.6 (=CHSi), 127.2 (o-C of C6H4CH3), 128.9
(m-C of C6H4CH3), 129.1 (ipso-C at CH3 of C6H4CH3), 137.8
(=CHC6H4CH3), 149.3 (=CHAr); 29Si NMR (C6D6): d=
À67.40, À67.85 (core), À79.27 (=CHSi); APPI-MS: m/z
([M+H]+, % intensity)=933 (100), 934 (76), 935 (59), 936
(30), 937 (15), 938 (6); anal. calcd. for C37H72O12Si8 (%): C
47.60, H 7.77; found: C 47.41, H 7.82; mp 184–1868C.
J=17.2 Hz, =CHSi), 7.15 (pseudo t, 2H, Ar), 7.28 (pseudo t,
2H, Ar), 7.62 (d, 2H, J=8.2 Hz, Ar), 7.84 (d, 1H, J=
17.2 Hz=CHN), 7.85 (d, J=7.64 Hz, 2H, Ar); 13C NMR
(C6D6): d=23.0, 23.1 (CH2), 24.3, 24.4 (CH), 25.9, 26.0
(CH3), 110.9, 111.3, 120.5, 121.7, 125.1, 126.7 (Ar), 138.6
(=CHSi), 139.7 (=CHN); 29Si NMR (C6D6): d=À67.20,
À67.63 (core), À77.63 (=CHSi); APPI-MS: m/z (overlaid
M+· and [M+H]+ profiles, % intensity)=1007 (92), 1008
(100), 1009 (81), 1010 (52), 1011 (25), 1012 (9); anal. calcd.
for C42H73NO12Si8 (%): C 50.01, H 7.29; found: C 50.12, H
7.33; mp 186–1878C.
Mixture of isomers 7f/8f=7/1: d=1H NMR (C6D6): d=
0.80–0.88 (m, 14H, CH2), 1.04–1.11 (m, 42H, CH3), 2.00–
2.18 (m, 7H, CH), 3.30 (dd, 2H, J=6.2 Hz, 1.6 Hz,
=CHCH2), 3.78 (d, J=7.6 Hz, =CHCH2 in 8f), 5.73 (dt, par-
tially overlapped, J=14.0 Hz, 1.1 Hz, =CHC6H5 in 8f), 5.74
(dt, 1H, J=18.6, 1.7 Hz, =CHSi), 6.56 (dt, J=14.1 Hz,
7.6 Hz, =CHCH2 in 8f), 6.82 (dt, 1H, J=18.6 Hz, 6.2 Hz,
=CHCH2), 7.01–7.2 (m, 5H, Ph), 7.56 (d, 1H, J=19.2 Hz,
=CHPh); 13C NMR (C6D6): d=22.9, 23.1 (CH2), 24.3, 24.4
(CH), 25.9, 26.0 (CH3), 118.6 (=CHSi), 127.1, 128.9, 129.0
(C6H5), 137.8 (ipso-C of C6H5), 149.3 (=CHPh); 13C NMR
(C6D6): d=22.9, 23.0 (CH2), 24.3, 24.4 (CH), 25.9, 26.0
(CH3), 43.0 (CH2C6H5), 121.7 (=CHSi), 126.5, 128.8, 129.1
(C6H5), 139.2 (ipso-C of C6H5), 151.6 (=CHPh); 29Si NMR
(C6D6): d=À67.49, À67.64, À67.84, À67.90 (core), À80.55
(=CHSi); APPI-MS: m/z (overlaid M+· and [M+H]+ pro-
files, % intensity)=932 (25), 933 (100), 934 (62), 935 (44),
936 (24), 937 (11), 938 (4); 116–1198C.
Acknowledgements
Financial support from the National Centre for Research and
Development (Poland), (project No. NR 05 0005 04/2008) is
gratefully acknowledged. P. Zak wishes to acknowledge the
grant from the Operational Programme of Human Resour-
ces, Action 8.2., co-financed by EU European Social Fund
and Polish State.
˙
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7g: H NMR (C6D6): d=À0.04 (s, 9H, SiMe3), 0.83–0.87
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(100), 930 (88), 931 (69), 932 (41), 933 (24), 934 (9); anal.
calcd. for C34H76O12Si9 (%): C 43.92, H 8.24; found: C 43.94,
H 8.40; mp 135–1368C.
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1.13 (m, 42H, CH3), 1.16–1.33 (m, 2H, CH3CH2), 1.36–1.42
(m, 2H, CH3CH2CH2), 2.06–2.19 (m, 7H, CH), 3.39 (t, 2H,
J=6.5 Hz, CH2O cis), 3.48 (t, 2H, J=6.5 Hz, CH2O trans),
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[OACHTUNGTRENNUNG(CH2)3CH3], 19.4 [OACHTUNTGRENN(NGU CH2)2CH2CH3], 23.0, 23.1 (CH2),
24.3, 24.4 (CH), 25.9, 26.0 (CH3), 31.1 (OCH2CH2), 68.0
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Adv. Synth. Catal. 2009, 351, 2675 – 2682