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We report herein the development of an S-atom transfer process using triethyl phosphite as the S-atom acceptor that allows thiols to serve as precursors of C-centered radials. A range of functionalized and electronically unbiased alkenes including those containing common heteroatom-based functional groups. This process is driven by the exchange of relatively weak S-H and C-S bonds of aliphatic thiols for C-H, C-C, and S-P bonds of the products formed.

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