Light-driven utilization of CO2 in organic synthesis is highly attractive because it mimics nature. However, such transformations are mainly limited to the incorporation of only a single CO2 molecule into organic compounds, far less than the number of CO2 molecules fixed in the product in photosynthesis. Here we report the visible-light photoredox-catalysed dicarboxylation of alkenes, allenes and (hetero)arenes with the incorporation of two CO2 molecules. This method realizes the formation of multiple C–C bonds with high chemo- and diastereoselectivities under mild conditions, which represents a simple, rapid and sustainable approach to valuable dicarboxylic acids. Moreover, this transition-metal-free protocol exhibits a low catalyst loading, good functional group tolerance, broad substrate scope, facile scalability and easy product derivatizations to give drug and material molecules. Mechanistic studies indicate a pathway by which a visible-light-induced two-electron reduction via sequential single electron transfer generates radical anions of such unsaturated substrates, broadening the repertoire of strategies.
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Details about materials and methods, experimental procedures, mechanistic studies, characterization data and NMR spectra are available in the Supplementary Information. Additional data are available from the corresponding author upon reasonable request. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: (E)-2aw (CCDC 1922731), cis-8a-Me (CCDC 1956271) and trans-8k′-Me (CCDC 1968028), These data can be obtained free of charge from www.ccdc.cam.ac.uk/data_request/cif.
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We thank S. Ma and H. Qian (Fudan University) for their samples of allenes, valuable discussion and suggestions. We also thank R. Martin (ICIQ) and J. J. Chruma (Sichuan University) for valuable discussion and help. Financial support was provided by the National Natural Science Foundation of China (21822108, 21772129), the Fok Ying Tung Education Foundation (161013), Sichuan Science and Technology Program (20CXTD0112), Beijing National Laboratory for Molecular Sciences (BNLMS201903), Fundamental Research Funds from Sichuan University (2020SCUNL102), and the Fundamental Research Funds for the Central Universities. We also thank X. Wang from the Analysis and Testing Center of Sichuan University and the comprehensive training platform of the Specialized Laboratory in the College of Chemistry at Sichuan University for compound testing.
A patent on this work has been filed in China under patent application number 201910319124.9.
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Ju, T., Zhou, YQ., Cao, KG. et al. Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis. Nat Catal 4, 304–311 (2021). https://doi.org/10.1038/s41929-021-00594-1