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Radical approaches to C–S bonds

Nature Reviews Chemistry volume 7, pages 573–589 (2023)Cite this article

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Abstract

Organosulfur functionalities are ubiquitous in nature, pharmaceuticals, agrochemicals, materials and flavourants. Historically, these moieties were introduced almost exclusively using ionic chemistry; however, radical-based methods for the installation of sulfur-based functional groups have recently come to the fore. These radical methods have enabled their late-stage introduction into complex molecules, avoiding the need to preserve labile organosulfur moieties through multistep synthetic sequences. Here, we discuss homolytic C–S bond-forming processes, with a particular emphasis on radical substitution approaches to sulfide, disulfide and sulfinyl products, and the use of sulfur dioxide and its surrogates to build sulfonyl products. We also highlight the mechanistic considerations that we hope will guide further development of radical-based strategies compatible with the various organosulfur moieties that feature in modern chemistry.

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Fig. 1: The diversity of organosulfur moieties is underpinned by their multiple oxidative states, leading to extensive applications but challenges in their construction.
Fig. 2: Radical strategies to sulfides.
Fig. 3: Sulfide synthesis by homolytic substitution.
Fig. 4: Disulfide synthesis by homolytic substitution.
Fig. 5: Substitution and addition in sulfinylation and sulfonylation chemistry.
Fig. 6: Opportunities for future research in radical sulfuration.

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This work was supported by the Natural Sciences and Engineering Research Council of Canada (RGPIN-2022-05058).

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    Zijun Wu & Derek A. Pratt

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Wu, Z., Pratt, D.A. Radical approaches to C–S bonds. Nat Rev Chem 7, 573–589 (2023). https://doi.org/10.1038/s41570-023-00505-x

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