1.3 Copper-Catalyzed Alkene Difunctionalization

Abstract Alkene difunctionalization is a classic molecular transformation in organic synthesis, enabling the production of more-complex molecules from simple hydrocarbon-derived feedstocks. Alkene difunctionalizations catalyzed by copper complexes offer potentially more-sustainable protocols compared to those catalyzed by more-precious or -toxic metals. This chapter summarizes important recent advancements in the field, especially in the area of asymmetric catalysis. A number of copper-catalyzed intramolecular and intermolecular alkene difunctionalizations for the synthesis of cyclic and acyclic chiral amines and ethers, and related compounds, are presented. The reactions include alkene and/or diene hydroamination, hydroetherification, carboamination, carboetherification, diamination, oxyamination, and dicarbofunctionalization. Many of the reaction mechanisms involve a radical component either in the first or second bond-forming event. The ability of copper to engage with radicals in bond-forming events, including enantioselective ones, is a valuable aspect of many of these reactions.