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Radical‐Transfer Hydroamination of Olefins with N‐Aminated Dihydropyridines
Author(s) -
Chou ChihMing,
Guin Joyram,
MückLichtenfeld Christian,
Grimme Stefan,
Studer Armido
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201000881
Subject(s) - hydroamination , chemistry , markovnikov's rule , radical , steric effects , reagent , catalysis , combinatorial chemistry , amination , selectivity , organic chemistry , regioselectivity
Abstract An efficient synthesis of N ‐phthalimidyl, benzamidyl, acetamidyl, carbamoyl, and ureayl derivatives of dihydropyridines and the application of these reagents as precursors for N‐centered radicals are presented. These aminated dihydropyridines could be used in radical‐transfer hydroamination reactions of various electron‐rich as well as nonactivated olefins in the presence of thiols as polarity‐reversal catalysts. These reactions worked without the aid of any transition metal. Steric and electronic effects exerted by the N‐substitutents of the N‐centered radicals are discussed. In contrast to most metal‐catalyzed processes, the radical hydroamination delivered the opposite regioisomer with excellent anti‐Markovnikov selectivity. Hydroamination products were obtained as protected amines that are readily isolated.