Mechanistic Aspects of Hydrosilane/Potassium tert-Butoxide (HSiR3/KOtBu)-Mediated Reactions

摘要

The hydrosilane/potassium tert -butoxide reagent system has attracted significant attention over the last 5 years since the discovery of its ability to silylate heteroarene C–H bonds. Numerous useful HSiR_(3)/KO~(t) Bu-mediated transformations are now known, including silylation of sp, sp~(2), and sp~(3) C–H bonds, reductive cleavage of C–O, C–S, and C–N bonds, reduction of polycyclic arenes, and hydrosilylation and polymerization of styrenes. This mini-review surveys the rich diversity of reaction mechanisms, both ionic and free radical and including hydride transfer, H atom transfer, and electron transfer, that have been uncovered during recent studies on the HSiR_(3)/KO~(t) Bu reagent system. Several mechanistic phenomena that remain to be explained are also highlighted.