211812-14-5Relevant articles and documents
Anti-Markovnikov Radical Hydro- and Deuteroamidation of Unactivated Alkenes
Jiang, Heng,Studer, Armido
, p. 7105 - 7109 (2019)
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 H2O to the alkyl radical intermediate. Accordingly, deuteroamidation of alkenes was realized with excellent D incorporation by using D2O 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.
Amidyl Radicals by Oxidation of α-Amido-oxy Acids: Transition-Metal-Free Amidofluorination of Unactivated Alkenes
Jiang, Heng,Studer, Armido
supporting information, p. 10707 - 10711 (2018/08/17)
A three-component transition-metal-free amidofluorination of unactivated alkenes and styrenes is presented. α-Amido-oxy acids are introduced as efficient and easily accessible amidyl radical precursors that are oxidized by a photoexcited organic sensitizer (Mes-Acr-Me) to the corresponding carboxyl radical. Sequential CO2 and aldehyde/ketone fragmentation leads to an N-centered radical that adds to an alkene. Commercial Selectfluor is used to trap the adduct radical through fluorine-atom transfer. The transformation features by high functional-group tolerance, broad substrate scope, and practical mild conditions. Mechanistic studies support the radical nature of the cascade.
