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Anti‐Markovnikov Radical Hydro‐ and Deuteroamidation of Unactivated Alkenes
Author(s) -
Jiang Heng,
Studer Armido
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901566
Subject(s) - markovnikov's rule , chemistry , alkene , electrophile , thiophenol , catalysis , organic chemistry , adduct , reagent , combinatorial chemistry , radical ion , photochemistry , radical , medicinal chemistry , regioselectivity , ion
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 H 2 O to the alkyl radical intermediate. Accordingly, deuteroamidation of alkenes was realized with excellent D incorporation by using D 2 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.