Direct Stereospecific Deoxyamination of Alcohols Enabled by Li-Mediated SuFEx.

Optically active nitrogen-bearing molecules are central to drug discovery, which has driven the development of efficient, stereocontrolled C(sp3)-N bond-forming methods. Herein we report a SuFEx-enabled platform that directly couples diverse alcohols and free N-nucleophiles via deoxygenative C(sp3)-N(sp3/sp2) bond formation with high stereospecificity without elimination. Using an inexpensive lithium triflate salt to suppress competitive deoxyfluorination, this method enables facile deoxyamination with broad substrate scope, N-heterocycle synthesis, late-stage functionalization, and stereodivergent synthesis of pharmaceuticals.