Effects of Silyl Substituents on the Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl)silanes and Their SE2′ Chirality Transfer Reactions



A series of axially chiral 4-substituted-1-silyl-2,3-butadienes [(allenylmethyl)silanes] were synthesized from 3-bromo-5-silylpenta-1,3-dienes by a Pd-catalyzed asymmetric reaction with a soft nucleophile. The optically active (allenylmethyl)silanes react with an acetal in the presence of TiCl4 to give the enantiomerically enriched 1,3-diene derivatives through an SE2′ pathway. Effects of the silyl groups on the enantioselectivity of the asymmetric allene synthesis and the subsequent SE2′ chirality transfer reaction were studied. It was found that as the steric bulk of the silyl groups in the 3-bromo-5-silylpenta-1,3-dienes was increased from -SiMe3 to -SiiPr3, the enantioselectivity of the two enantioselective processes also improved.