Collect. Czech. Chem. Commun. 1980, 45, 2808-2816

Enantioselective hydrosilylation of tert-butyl phenyl ketone by diphenylsilane catalysed by [Rh{(-)-DIOP}2]+ClO4-

Ivan Kolb and Jiří Hetflejš

Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol


Kinetics of the title reaction has been studied by the method of initial reaction rates. In the presence of free chiral ligand the hydrosilylation was found to be first order in the catalyst and in the ketone and fractional order in the organosilicon hydride. The rate data and the results of spectroscopic study of interaction of diphenylsilane with the rhodium complex have been interpreted in terms of a reaction model involving formation of the corresponding cationic silyl(hydrido)rhodium complex followed by interaction of the ketone with this complex in the rate determining step. The results are confronted with those obtained for the analogous reaction catalysed by [Rh(1,5-COD)(-)-DIOP]+ClO4-.