Reaction design strategies for organocatalytic CO2 valorization: Control of reactivity and selectivity with implications for asymmetric synthesis

Carbon dioxide (CO 2 ) is a thermodynamically stable yet versatile C1 feedstock whose reactivity can be accessed through catalytic design. Recent advances in organocatalysis have shifted CO 2 conversion from a focus on activation feasibility to control over reactive intermediates and selectivity. Visible-light photoredox catalysis and radical relay strategies enable single-electron activation pathways, allowing C–H carboxylation, cascade difunctionalization, radical anion processes, and transient CO 2 -mediated protection under mild, metal-free conditions. Beyond activation through energetic input, control of noncovalent interactions, confined catalytic environments, and cooperative Lewis acid–base systems enable stereocontrolled CO 2 incorporation. From hydrogen-bond-driven enantioselective cyclizations and chalcogen-bond activation to stereodivergent photocatalysis, substrate-controlled transformations, and enantioselective carbon isotope exchange, these developments demonstrate controlled CO 2 incorporation across diverse reaction pathways and modes of selectivity. This review summarizes recent advances in organocatalytic CO 2 utilization, emphasizing the integration of activation modes, control over reactive intermediates and selectivity, and sustainable reaction design.