π-Allyl Donicity Switch in Catalytic Asymmetric Allylation: Usability of a Robust and Feasible Allyl Methyl Ether

摘要

A chiral CpRu(II)/p-TsOH combined catalyst is described for asymmetric allylation that reverses the π-allyI donicity of AUX (All: allyl, X: leaving group) from "AIIOAc > AllOPh > AI10H > AllOMe" to "AllOH > AIIOMe > AllOPh > AIIOAc". This represents a novel deviation from conventional Tsuji-Trost-Pd-based methods that operate under basic conditions. This is the first successful demonstration of endowing reactivity in chemically stable AIIOMe, which should significantly expand the scope of synthetic possibilities.