Anti-Markovnikov Radical Hydro- and Deuteroamidation of Unactivated Alkenes.

Radical anti-Markovnikov hydro- and deuteroamidation of unactivated alkenes was achieved by merging photoredox and thiol catalysis. Reactions proceed by addition of the electrophilic CbzHN-radical (Cbz=carbobenzyloxy), readily generated by single-electron-transfer (SET) oxidation of an α-Cbz-amino-oxy acid to an alkene. The adduct radical is reduced by thiophenol added as an organic polarity reversal cocatalyst, which mediates the H transfer from H2 O to the alkyl radical intermediate. Accordingly, deuteroamidation of alkenes was realized with excellent D incorporation by using D2 O as the stoichiometric formal radical-reducing reagent. The reaction features low redox catalyst loading, excellent anti-Markovnikov selectivity, and the use of a large alkene excess is not required. Diverse Cbz-protected primary amines, including β-deuterated amines, can be obtained by applying this method.