Electrophotochemical Anti-Markovnikov Selective Carboxylation of Alkenes.

Carbon dioxide (CO2), as an ideal single-carbon source in chemical synthesis, has garnered extensive attention for its direct utilization. The direct conversion of CO2 via electrochemistry, an environmentally benign strategy, offers a crucial direction and immense potential for resource transformation in the context of carbon neutrality goals. However, due to the extremely low reduction potential of CO2 itself, the electrochemical carboxylation process often inevitably leads to the formation of multiple products, resulting in poor reaction selectivity. To tackle this challenge, a photoelectrochemical strategy is reported for the efficient reduction of CO2 and the anti-Markovnikov selective carboxylation of activated and unactivated alkenes. The reaction is simple to perform, requiring no additional chemical oxidants throughout the process. Experimental verification confirms that it exhibits excellent applicability to a wide range of alkene substrates, thereby providing a new pathway for highly selective and green carboxylation synthesis.