Umpolung Amide Synthesis Using Substoichiometric N‑Iodosuccinimide (NIS) and Oxygen as a Terminal Oxidant

direct access to amides from an α-bromo nitroalkane and an amine. Based on its mechanistic bifurcation after convergent C−N bond formation, depending on the absence or presence of oxygen, UmAS using substoichiometric N-iodosuccinimide (NIS) under aerobic conditions has been developed. In combination with the enantioselective preparation of α-bromo nitroalkane donors, this protocol realizes the goal of enantioselective α-amino amide and peptide synthesis based solely on catalytic methods. “Amide formation avoiding poor atom economy reagents”1 has been hailed as a high level challenge and in need of critical importance in organic chemistry due to the ubiquity of amide bonds in biologically active molecules.2 Currently, solid-phase peptide synthesis3 and native chemical ligation4 are the most used amide forming transformations involving stereochemicall