Rational design of catalysts for hydrocarboxylation with CO2 to afford C2+ carboxylic acids

Abstract

The hydrocarboxylation reaction is a sustainable and efficient method for transforming the ideal C₁ synthon carbon dioxide (CO₂) into valuable C₂₊ carboxylic acids, featuring high atom economy. However, these reactions typically entail a cascade catalytic process involving both CO₂ reduction and carbon–carbon (C–C) coupling. The rational design of transition metal catalysts, which can tailor both the reactivity and selectivity of the reaction, is critical for obtaining excellent catalytic results using diverse reductants. In this review, we focus on transition metal catalyzed hydrocarboxylation reactions of CO₂ with unsaturated hydrocarbons or oxygen-containing compounds to synthesize C₂₊ carboxylic acids, where metal powder, organometallic compounds, hydrosilanes, hydroboranes, hydrogen (H₂), and alcohols are utilized as reducing agents, separately. We also discuss the challenges and prospects of further research on hydrocarboxylation with CO₂.