Exploring asymmetric electrochemical atom transfer radical addition with chiral copper complexes

Abstract

Copper catalysed electrochemical atom transfer radical addition (eATRA) is a newly developed method allowing the formation of C–C bonds under mild conditions whereby an electro generated organocopper(II) species plays a key role. Considering recent developments in this emergent field, the exploration of an asymmetric variant of the reaction would be an advantage. Herein, reported is the synthesis of a new chiral ligand based on a biisoquinoline scaffold suitable for copper coordination. Structural properties of the corresponding copper(II) complexes have been evaluated, disclosing both square planar and square pyramidal geometries. Spectroscopic and electrochemical characterisation of these species demonstrated similarities with previously investigated complexes, and implementation to the eATRA reaction yielded moderate activities. While these explorations did not lead to detectable chiral induction, this work contributes to building a better understanding of the role that the organocopper(II) complex plays in this reaction.