Cross-Electrophile Coupling: Principles of Reactivity and Selectivity

Everson, D., and D. Weix. Cross-Electrophile Coupling: Principles of Reactivity and Selectivity. J. Org. Chem., 4798.
Abstract A critical overview of the catalytic joining of two different electrophiles, cross-electrophile coupling (XEC), is presented with an emphasis on the central challenge of cross-selectivity. Recent synthetic advances and mechanistic studies have shed light on four possible methods for overcoming this challenge: (1) employing an excess of one reagent; (2) electronic differentiation of starting materials; (3) catalyst-substrate steric matching; and (4) radical chain processes. Each method is described using examples from the recent literature.
Keywords allylic acetatesaryl halidesbond-dissociation energiesc-ccatalyzed reductive allylationnickel-complexesorganic halidestransition-metalsunactivated alkyl-halidesunsymmetrical biaryls
DOI 10.1021/jo500507s