Toward Sustainable Photo‐/Electrocatalytic Carboxylation of Organic Substrates with CO2

Abstract Historically, carbon dioxide found many applications in organic chemistry from reaction medium e. g., super critical carbon dioxide (scCO 2 ) or CO 2 ‐expanded liquid (CXL) system; extraction (natural products), separation (supercritical fluid chromatography); chemo‐, regio‐, and stereoselective transformation via the formation of transient intermediates i. e., carbonate, carbamate etc. Recently, researchers have exploited CO 2 as an inexpensive, renewable and non‐toxic C1 feedstock for carboxylation and carbonylation reactions. However, owing to its inherent kinetic and thermodynamic stability, most of the transformations require high temperatures, high pressure, and stoichiometric amounts of organometallic reductants that leads to accidental and environmental hazards. Inspired by the natural processes, photo‐ and electrocatalytic conversion of CO 2 into value‐added products has emerged as a benign and practical approach in organic synthesis. Here in this review, we will discuss some recent photo‐ and electrocatalytic methods and their comparison toward sustainable development.