Carboxylation Reactions with Carbon Dioxide Using N-Heterocyclic Carbene-Copper Catalysts

Abstract

The development of versatile catalyst systems and new transformations for the utilization of carbon dioxide (CO₂ ) is of great interest and significance. This Personal Account reviews our studies on the exploration of the reactions of CO₂ with various substrates by the use of N-heterocyclic carbene (NHC)-copper catalysts. The carboxylation of organoboron compounds gave access to a wide range of carboxylic acids with excellent functional group tolerance. The C-H bond carboxylation with CO₂ emerged as a straightforward protocol for the preparation of a series of aromatic carboxylic esters and butenoates from simple substrates. The hydrosilylation of CO₂ with hydrosilanes provided an efficient method for the synthesis of silyl formate on gram scale. The hydrogenative or alkylative carboxylation of alkynes, ynamides and allenamides yielded useful α,β-unsaturated carboxylic acids and α,β-dehydro amino acid esters. The boracarboxylation of alkynes or aldehydes afforded the novel lithium cyclic boralactone or boracarbonate products, respectively. The NHC-copper catalysts generally featured excellent functional group compatibility, broad substrate scope, high efficiency, and high regio- and stereoselectivity. The unique electronic and steric properties of the NHC-copper units also enabled the isolation and structural characterization of some key intermediates for better understanding of the catalytic reaction mechanisms.

Keywords: N-heterocyclic carbene; alkynes; carbon dioxide; carboxylation; copper catalysts.