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

Abstract

A chiral CpRu(II)/p-TsOH combined catalyst is described for asymmetric allylation that reverses the π-allyl donicity of AllX (All: allyl, X: leaving group) from AllOAc > AllOPh > > to AllOH > AllOMe > AllOPh > AllOAc. 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 AllOMe, which should significantly expand the scope of synthetic possibilities.