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Updated: Jul 30, 2025

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Ni-Electrocatalytic Enantioselective Doubly Decarboxylative C(sp3)-C(sp3) Cross Coupling
Yang Gao1, Benxiang Zhang1, Jiayan He1
1Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Abstract:
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.
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