Ring Expansion of Epoxides under Bronsted Base Catalysis: Formal [3+2] Cycloaddition of β,γ-Epoxy Esters with Imines Providing 2,4,5-Trisubstituted 1,3-Oxazolidines

A novel ring-expansion reaction of epoxides under Bronsted base catalysis was developed. The formal [3+2] cycloaddition reaction of beta,gamma-epoxy esters with imines proceeds in the presence of triazabicyclodecene (TBD) as a superior Bronsted base catalyst to afford 2,4,5-trisubstituted 1,3-oxazolidines in a highly diastereoselective manner. This reaction involves the ring opening of the epoxides with the aid of the Bronsted base catalyst to generate alpha,beta-unsaturated esters having an alkoxide at the allylic position, which would formally serve as a synthetic equivalent of the 1,3-dipole, followed by a cycloaddition reaction with imines in a stepwise fashion. This methodology enables the facile synthesis of enantioenriched 1,3-oxazolidines from easily accessible enantioenriched epoxides.