Dirhodium(II)/DPPM Catalyzed 1,2-Hydrosilylation of Conjugated Dienes with Tertiary Silanes

A simple and efficient Rh₂(OAc)₄/DPPM (bis(diphenylphosphanyl)methane) catalyzed regioselective 1,2-anti-Markovnikov hydrosilylation of conjugated dienes with various tertiary silanes gave homoallylic silanes in acetonitrile, which tolerate broad functional groups. Control experiments proved that no π-allyl transition metal intermediates were involved in this 1,2-anti-Markovnikov hydrosilylation. Dirhodium hydride species was observed in hydrosilylation, suggesting that a direct insertion of the terminal double bond into a Rh-H bond is involved in this reaction.