Tuneable, in situ-generated nickel-hydride alkene isomerisation catalyst†

Abstract

A modular, operationally practical Ni(0)/silane alkene isomerisation system has been developed with air-tolerant reagents. An attractive feature of this method is the ability to rapidly screen a variety of N-heterocyclic carbene (NHC) ligands, enabling optimisation through ancillary ligand backbone modification for enhanced reactivity. This system is readily scalable (>1 g alkene) and tolerates a diverse array of functional groups in high E-selectivity, including aryl bromides, heterocycles, tertiary amines, and α,β-unsaturated amides. Preliminary mechanistic experiments support a Ni–H insertion/elimination pathway.