Direct Catalytic Asymmetric Addition of Alkylnitriles to Aldehydes with Designed Nickel-Carbene Complexes

Angew Chem Int Ed Engl. 2021 Apr 12;60(16):8739-8743. doi: 10.1002/anie.202016690. Epub 2021 Mar 10.

Abstract

A direct catalytic asymmetric addition of acetonitrile to aldehydes that realizes over 90 % ee is the ultimate challenge in alkylnitrile addition chemistry. Herein, we report achieving high enantioselectivity by the strategic use of a sterically demanding NiII pincer carbene complex, which afforded highly enantioenriched β-hydroxynitriles. This highly atom-economical process paves the way for exploiting inexpensive acetonitrile as a promising C2 building block in a practical synthetic toolbox for asymmetric catalysis.

Keywords: aldehydes; enantioselectivity; homogeneous catalysis; nickel; nitriles.