Mild Photochemical Reduction of Alkenes and Heterocycles via Thiol-Mediated Formate Activation

• Published in: Organic letters Vol. 26; no. 26; pp. 5534 - 5538
• Main Authors: Brzezinski, Carter U., LeBlanc, Andrew R., Clerici, Madeline G., Wuest, William M.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05-07-2024
• Subjects: Letter
• ISSN: 1523-7060; 1523-7052; 1523-7052
• DOI: 10.1021/acs.orglett.4c01894

The reduction of alkenes to their respective alkanes is one of the most important transformations in organic chemistry, given the abundance of natural and commercial olefins. Metal-catalyzed hydrogenation is the most common way to reduce alkenes; however, the use of H2 gas in combination with the precious metals required for these conditions can be impractical, dangerous, and expensive. More complex substrates often require extremely high pressures of H2, further emphasizing the safety concerns associated with these hydrogenation reactions. Here we report a safe, cheap, and practical photochemical alkene reduction using a readily available organophotocatalyst, catalytic thiol, and formate. These conditions reduce a variety of di-, tri-, and tetra-substituted alkenes in good yield as well as dearomatize pharmaceutically relevant heterocycles to generate sp3-rich isosteres of benzofurans and indoles. These formal-hydrogenation conditions tolerate a broad range of functionalities that would otherwise be sensitive to typical hydrogenations and are likely to be important for industry applications.