The effect of substituents at silicon on the cross-metathesis of trisubstituted vinylsilanes with olefins

Cross-metathesis of divinylsubstituted silanes and disiloxanes in the presence of Grubbs catalysts

“…Recently, we revealed that only vinylsilanes bearing at least two electron-withdrawing group at silicon can efficiently undergo cross-metathesis with olefins [8], while vinylsilane homometathesis was restricted only to dichloroderivatives ViSiCl 2 R where R = alkyl, aryl, OSiMe 3 [11]. Therefore, we tested a series of electron-withdrawing groups containing divinylsilanes (Fig.…”

“…(3)) and the metallacarbene mechanism (Eq. (4)), divinylbis(pentafluorophenyl)silane and 1,3-divinyl-1,1,3,3-tetraethoxydisiloxane were tested in the reac- tions with styrene-d 8 in the presence of II. In the case of the non-metallacarbene mechanism, the formation of styrylsilane-d 7 , bis(styryl)silane-d 14 and ethylene-d 1 is to be expected (Eq.…”

“…We have previously shown that Grubbs type catalysts effectively catalyse the cross-metathesis (CM) of trialkoxy-, trisiloxy- [5], trichloro-and generally electron-withdrawing group substituted vinylsilanes [6] and vinylsilsesquioxanes [7] with styrenes, alkenes and numerous allyl derivatives. Recently, we have proposed a general scheme of vinylsilane reactivity in the presence of Grubbs catalyst [8]. Despite the fast development in the study of reactivity of unsaturated organosilicon compounds, there are still limited data available on the reactivity of divinylsubstituted silanes and disiloxanes.…”

Transition metals in organic synthesis: Highlights for the year 2005

“…Homo-alkene-alkene CM of was described [1211,1212]. (224) Ruthenium catalyzed alkene-alkene CM of styrenes [1213], 1-allyl-tetrahydro-␤-carboline and -tetrahydroquinoline [1214], propenoic esters [1215,1216], alkenylsilanes [283,1217], allyl trimethylsilane [1218], conjugated dienes [1219,1220], allyl cyanide [1221], acrylonitrile [1222], ethenylazulene [1223], N-allylpyrimidines [1224], terminal 1-en-4-ols [644] and ␤-hydroxyenones [1225] with terminal alkenes were described.…”

Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene

“…The development of a family of ruthenium-based catalysts tolerant of the majority of functional groups and typical organic and polymer processing conditions has allowed a great number of new applications [7]. In the chemistry of unsaturated organosilicon compounds effective metathesis transformations have been described by our group for vinyltris(trimethylsiloxy)silane [8,9], chlorosubstituted vinyldisiloxanes [9] and vinylsubstituted silsesquioxanes [10]. ViSi-(OEt) 2 OSi(OEt) 2 Vi (Vi = H 2 C@CH-) can be metathetically copolymerized with 1,9-decadiene [11,12] or divinylbenzene [13] and undergoes ROM/ADMET copolymerization with cyclooctadiene [11].…”