Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp3)–C(sp3) Cross Coupling

The first examples of enantioselective doubly decarboxylative cross coupling are disclosed. Malonate half amides are smoothly coupled to a variety of primary carboxylic acids after formation of the corresponding redox-active esters under Ni-electrocatalytic conditions using a new chiral ligand based on PyBox, resulting in amides with α-alkylated stereocenters. The scope of the reaction is broad, tolerating numerous functional groups, and uniformly proceeds with high ee. Finally, the potential utility of this enantioselective radical–radical reductive cross coupling to simplify synthesis is demonstrated with numerous case studies.