Hydrosilylation of acetophenone with diphenylsilane in the presence of rhodium(I) complexes with chiral amines

New chiral rhodium complexes cis -[Rh(CO) 2 (RNH 2 )Cl] [RNH 2 = ( R )-(−)- cis -MyrtNH 2 , ( R )-(−)-MenthylNH 2 , ( R )-(+)-BornylNH 2 ] were synthesized and their catalytic properties in reactions of hydrosilylation of acetophenone with diphenylsilane were studied. It was shown that the reaction products were diphenyl-1-phenylethoxysilane, diphenyl-1-phenylvinyloxysilane and 1,1,3,3-tetraphenyldisiloxane. The best catalytic activity displayed (−)- cis -[Rh(CO) 2 (MenthNH 2 )Cl]. The hydrosilylation of acetophenone with diphenylsilane in the presence of [Rh(CO) 2 (μ-Cl)] 2 and [Rh(cod)Cl] 2 and amines in situ was studied. The best ratio amine:complex = 5:1 was established. With the catalytic systems based on [Rh(cod)Cl] 2 or [Rh(CO) 2 (μ-Cl)] 2 the activity increased in the series of amines: ( R )-(−)- cis -MyrtNH 2 < ( R )-(−)-MenthylNH 2 < ( R )-(+)-BornylNH 2 , and ( R )-(−)-MenthylNH 2 < ( R )-(+)-BornylNH 2 < ( R )-(−)- cis -MyrtNH 2 , respectively. The chemoselectivity maximum was observed in the presence of [Rh(cod)Cl] 2 with ( R )-(−)-MenthylNH 2 and [Rh (CO) 2 (μ-Cl)] 2 with ( R )-(+)-BornylNH 2 ; maximum asymmetric induction was 43.5% ee at the use of [Rh(CO) 2 (μ-Cl)] 2 and ( R )-(+)-BornylNH 2 .