Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

Carbon dioxide (CO₂) is one of the most important materials as renewable chemical feedstock. In this review, the Co- and Rh-catalyzed transformation of CO₂ via carbon-carbon bond-forming reactions is summarized. Combinations of metals (cobalt or rhodium), substrates, and reducing agents realize efficient carboxylation reactions using CO₂. The carboxylation of propargyl acetates and alkenyl triflates using cobalt complexes as well as the cobalt-catalyzed reductive carboxylation of α,β-unsaturated nitriles and carboxyamides in the presence of Et₂Zn proceed. A Co complex has been demonstrated to act as an efficient catalyst in the carboxylation of allylic C(sp³)-H bonds. Employing zinc as the reductant, carboxyzincation and the four-component coupling reaction between alkyne, acrylates, CO₂, and zinc occur efficiently. Rh complexes also catalyze the carboxylation of arylboronic esters, C(sp²)-H carboxylation of aromatic compounds, and hydrocarboxylation of styrene derivatives. The Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and CO₂ proceeds to afford pyrones.