Synthesis and application of a dual chiral [2.2]paracyclophane-based N-heterocyclic carbene in enantioselective β-boration of acyclic enones

Abstract

An enantioselective conjugate addition of boron to α,β-unsaturated ketones catalysed by either a N-heterocyclic carbene or a copper–carbene complex generated in situ from a new chiral bicyclic triazolium based on [2.2]paracyclophane is presented. The dual chiral carbene–copper catalyst has significant advantages over its carbene counterpart as an organocatalyst in asymmetric β-boration of acyclic enones, giving a variety of chiral β-boryl ketones in good yields and enantioselectivities. This is a successful example of employing the same N-heterocyclic carbene in one catalytic reaction as both an organocatalyst and a ligand for transition metal catalysis.