Markovnikov-Selective Hydrosilylation of Electron-Deficient Alkenes with Arylsilanes Catalyzed by Mono(phosphine)palladium(0)

作者：Komine Nobuyuki^*; Abe Makoto; Suda Ryoko; Hirano Masafumi

来源：Organometallics, 2015, 34(2): 432-437.

DOI：10.1021/om500964g

Markovnikov-selective hydrosilylation of electron-deficient alkenes with HSiPh3 is catalyzed by a mono(phosphine)palladium(0) complex, Pd(eta(2):eta(2)-C6H10O)(PMe3) (1a). The hydrosilylation of acrylonitrile with HSiPh3 at 30 degrees C proceeds to completion within 40 min in the presence of 5 mol % of 1a. The complex 1a also shows the catalytic activity for the hydrosilylation with mono- and diarylsilanes and monochlorosilane such as HSiPhMe2, HSiPh2Me, and HSiClMe2. The hydrosilylation using para-substituted styrenes clearly shows the electron-withdrawing substituent promoting the reaction. Mechanistic studies indicate that the reaction is proceeding by a Chalk-Harrod mechanism with the reductive elimination of an (alkyl)(silyl)palladium(II) intermediate being the rate-determining step.

• 出版日期2015-1-26