Generation and Reactivity of Amidyl Radicals: Manganese‐Mediated Atom‐Transfer Reaction
Run‐Zhou Liu, Jinxia Li, Jun Sun, Xian‐Guan Liu, Shuanglin Qu, Ping Li, Bo Zhang
Abstract
Abstract A simple and efficient protocol to generate amidyl radicals from amine functionalities through a manganese‐mediated atom‐transfer reaction has been developed. This approach employs an earth‐abundant and inexpensive manganese complex, Mn 2 (CO) 10 , as the catalyst and visible light as the energy input. Using this strategy, site‐selective chlorination of unactivated C(sp 3 )−H bonds of aliphatic amines and intramolecular/intermolecular chloroaminations of unactivated alkenes were readily realized under mild reaction conditions, thus providing efficient access to a range of synthetically valuable alkyl chlorides, chlorinated pyrrolidines, and vicinal chloroamine derivatives. These practical reactions exhibit a broad substrate scope and tolerate a wide array of functional groups, and complex molecules including various marketed drug derivatives.