Functionalization of octavinylsilsesquioxane by ruthenium-catalyzed silylative coupling versus cross-metathesis.
Functionalization of octavinylsilsesquioxane (Vi(8)T(8), 1) by two reactions catalyzed by ruthenium complexes is reported: a silylative coupling reaction catalyzed by [RuHCl(CO)(PCy(3))(2)] (I) and cross-metathesis catalyzed by first- (II) and second-generation (III) Grubbs' catalysts. The two reactions of 1 with styrene take place highly regio- and stereoselectively (the X-ray structure of the product 2 has also been obtained); the cross-metathesis of 1-hexene and allyltrimethylsilane occurs quite effectively, whereas the silylative coupling with these compounds gives a mixture of isomers. Functionalization of 1 with heteroatom-substituted vinyl derivatives (Si, O, N) by silylative coupling reaction has been found to be highly efficient, but cross-metathesis appears to be the more effective method for the synthesis of S-substituted vinyl-silsesquioxane.
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland. marcinb@main.amu.edu.pl
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Itami
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Marciniec
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Kubicki
D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D009942:Organometallic Compounds; D014753:Vinyl Compounds; D012428:Ruthenium