Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp 3 )-C(sp 3 ) 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.