Sequential Catalytic Isomerization and Allylic Substitution.Conversion of Racemic Branched Allylic Carbonates to Enantioenriched Allylic Substitution Products

摘要

We report a sequence of two catalytic processes occurring through metal-allyl intermediates that leads to enantioselective substitution of branched allylic esters with nitrogen,oxygen,and carbon nucleophiles.This process lies at the intersection of developments in sequential catalytic processes and the challenge of controlling both regioselectivity and enantioselectivity in allylic substitution.Enantioselective allylic substitution of branched allylic electro-philes is desirable because these reagents are easily prepared from a vinyl Grignard reagent and the wide array of available aldehydes.