Cobalt-catalyzed regioselective stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes.

ABSTRACT: We report the first stereoconvergent Markovnikov 1,2-hydrosilylation of conjugated dienes using catalysts generated from bench-stable Co(acac)₂ and phosphine ligands. A wide range of E/Z-dienes underwent this Markovnikov 1,2-hydrosilylation in a stereoconvergent manner, affording (E)-allylsilanes in high isolated yields with high stereoselectivities (E/Z = >99 : 1) and high regioselectivities (b/l up to > 99 : 1). Mechanistic studies revealed that this stereoconvergence stems from a σ-π-σ isomerization of an allylcobalt species generated by the 1,4-hydrometalation of Z-dienes. In addition, a cobalt catalyst that can only catalyze the hydrosilylation of the E-isomer of an (E/Z)-diene was identified, whic

SUBMITTER: Sang HL 

PROVIDER: S-EPMC5873224 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature