Catalytic Enantioselective Allylic Alkylative Desymmetrization, Carbon-Carbon and Carbon-Heteroatom Bond Forming Reactions

Abstract

In summary, we have developed a catalytic enantioselective desymmetrization of prochiral 1,3-dinitropropanes, which proceeds via enantiogroup differentiating allylic alkylation reaction. Functionalized allylic carbonates were used as the allyl source and the densely functionalized products consisting of two vicinal stereocenters were obtained through acyclic stereocontrol generally with good to excellent diastereoselectivity (up to >20:1 dr) and superb enantioselectivity (up to >99:1 er). The utility of the desymmetrized products was demonstrated through synthetic manipulations leading to an alkylidene butyrolactam and a unique dihydropyrazole derivative