biostudies-literatureShi QNational Natural Science Foundation of ChinaShanghai Jiao Tong University4453https://www.ebi.ac.uk/biostudies/studies/S-EPMC9343372biostudies-literatureUnknown13(1)Site- and enantioselective incorporation of deuterium into organic compounds is of broad interest in organic synthesis, especially within the pharmaceutical industry. While catalytic approaches relying on two-electron reaction manifolds have allowed for stereoselective delivery of a formal deuteride (D^-) or deuteron (D⁺) at benzylic positions, complementary strategies that make use of one-electron deuterium atom transfer and target non-benzylic positions remain elusive. Here we report a photochemical approach for asymmetric radical deuteration by utilizing readily available peptide- or sugar-derived thiols as the catalyst and inexpensive deuterium oxide as the deuterium source. This metal-free platform enables four types of deuterofunctionalization reactions of exocycNature communicationsVisible-light mediated catalytic asymmetric radical deuteration at non-benzylic positions.PMC934337222001163Ramanathan DXu MChang RShi QFunes-Ardoiz IPenin BYe JfalseVisible-light mediated catalytic asymmetric radical deuteration at non-benzylic positions.Site- and enantioselective incorporation of deuterium into organic compounds is of broad interest in organic synthesis, especially within the pharmaceutical industry. While catalytic approaches relying on two-electron reaction manifolds have allowed for stereoselective delivery of a formal deuteride (D^-) or deuteron (D⁺) at benzylic positions, complementary strategies that make use of one-electron deuterium atom transfer and target non-benzylic positions remain elusive. Here we report a photochemical approach for asymmetric radical deuteration by utilizing readily available peptide- or sugar-derived thiols as the catalyst and inexpensive deuterium oxide as the deuterium source. This metal-free platform enables four types of deuterofunctionalization reactions of exocyc2022-01-01T00:00:00Z2022 Aug2025-04-22T01:48:56.179Z2025-04-05T20:08:42.865ZS-EPMC93433723591511910.1038/s41467-022-32238-8