11族金属触媒におけるσ結合メタセシス反応を基軸とする合成反応

抄録

New fundamental reactions of organometallic compounds can often be a rich source of new synthetic reactions. We found σ-bond metathesis of M-X bonds in group 11 metal compounds with Si-H, Si-Si and B-B bonds. Through these reactions, several intermediates such as borylcopper(I), silylcopper(I), gold(I) hydride species, which otherwise are not easily accessible, can be generated and incorporated into catalytic reactions.We report a novel and versatile method for the synthesis of allylboronates through γ-selective substitution of allylic carbonates with diboron in the presence of a Cu (I)-phosphine catalyst. The Cu(I)-catalyzed reaction includes formal nucleophilic reaction of borylcopper(I) intermediates to allylic carbonates. The approach involving the reaction of borylcopper(I) intermediates has been further expanded to enantioselective synthesis of both optically active α-chiral allylboronates and B, Si-bifunctional cyclopropanes.Copper(I) catalysis based on a-bond metathesis of hydrosilanes and disilanes with copper(I) complex offers new synthetic methods for various organosilanes. Gold(I) catalysis involving gold (I) hydride species is also reported.