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

A simple and efficient Rh 2 (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.