When organolithiums meet imine reductases: a hybrid chemoenzymatic route towards chiral N-heterocycles.

A hybrid chemoenzymatic protocol for the stereoselective preparation of chiral 2-substituted azacycles is reported. Our methodology relies on a cyclization/bioreduction sequence promoted by organolithium reagents and imine reductase (IRED) enzymes, working under air and at room temperature, with three consecutive C-C/C-N/C-H bond formation events occurring in a one-pot, telescoped synthetic operation.