Deconstructive Carboxylation of Activated Alkenes with Carbon Dioxide

Abstract Carboxylation with carbon dioxide (CO 2 ) represents one notable methodology to produce carboxylic acids. In contrast to carbon–heteroatom bonds, carbon–carbon bond cleavage for carboxylation with CO 2 is far more challenging due to their inherent and less favorable orbital directionality for interacting with transition metals. Here we report a photocatalytic protocol for the deconstructive carboxylation of alkenes with CO 2 to generate carboxylic acids in the absence of transition metals. It is emphasized that our protocol provides carboxylic acids with obviously unchanged carbon numbers when terminal alkenes were used. To show the power of this strategy, a variety of pharmaceutically relevant applications including the modular synthesis of propionate nonsteroidal anti‐inflammatory drugs and the late‐stage carboxylation of bioactive molecule derivatives are demonstrated.