Heterogeneous Photocatalytic C(sp2)−H Activation of Formate for Hydrocarboxylation of Alkenes

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Abstract
Light‐driven carboxylation offers a promising approach for synthesizing valuable fine chemicals under mild conditions. Here we disclose a heterogeneous photocatalytic strategy of C(sp2)−H activation of formate for hydrocarboxylation of alkenes over zinc indium sulfide (ZnIn2S4) under visible light. This protocol functions well with a variety of substituted styrenes with good to excellent yields; it also works for unactivated alkenes albeit with lower yields. Mechanistic studies confirm the existence of CO2⋅− as a key intermediate. It was found that C(sp2)−H activation of formate is induced by S⋅ species on the surface of ZnIn2S4 via hydrogen atom transfer (HAT) instead of a photogenerated hole oxidation mechanism. Moreover, both cleavage of the C(sp2)−H of HCOO− and formation of a benzylic anion were found to be involved in the rate‐determining step for the hydrocarboxylation of styrene.
Funding Information
  • National Natural Science Foundation of China (22202007)
  • Fundamental Research Funds for the Central Universities of Beijing University of Chemical Technology (buctrc202210)

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