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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