A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross-coupling between alkyl-carboxylic acids and boronic acids is described. This Ni-catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox-active ester derivatives, specifically N-hydroxy-tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2•6H2O – $9.5/mol, Et3N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption.

This work bridges a gap in the cross‐coupling of aliphatic redox‐active esters with aryl zinc reagents. Previously limited to primary, secondary, and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using nickel catalysis. The scope of this operationally simple method is broad, and it can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers.

<div> <div> <div> <p>This work bridges a gap in the cross-coupling of aliphatic redox-active esters with aryl zinc reagents. Previously limited to primary, secondary and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using Ni-catalysis. The scope of this operationally simple method is broad and can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers. </p> </div> </div> </div>