Enantioselective, Aerobic Copper-Catalyzed Intramolecular Carboamination and Carboetherification of Unactivated Alkenes

Reduction of waste is an important goal of modern organic synthesis. We report herein oxidase reactivity for enantioselective intramolecular copper-catalyzed alkene carboamination and carboetherification reactions where previously used stoichiometric MnO 2 has been replaced with oxygen. This substitution was risky as the reaction mechanism is thought to involve C-C bond formation via addition of alkyl carbon radicals to arenes. Such intermediates are also susceptible to C-O bond formation via O 2 addition. Control of absolute stereochemistry under aerobic conditions was also uncertain. The oxidative cyclization efficiencies appear to track with the ease of the radical addition to the arenes.