Copper-Catalyzed Diastereoselective Addition of Diborylmethane to N-tert-Butanesulfinyl Aldimines: Synthesis of β-Aminoboronates

Abstract

We have developed a highly chemo- and diastereoselective alkylation of N-tert-butanesulfinyl aldimines with diborylmethane. Whereas the addition of diborylmethane under metal-free conditions shows poor diastereoselectivity, the use of a copper catalyst and a bidentate phosphine ligand significantly enhances the diastereoselectivity, providing chiral beta-aminoboronates in good yields. On the basis of the stereochemical outcome, we propose that the reaction likely proceeds via a boron-chelating six-membered chairlike transition state.