Single-Electron Palladium Catalysis Enables Tandem Amidyl-Radical Cyclization/Radical Heck-Type Coupling to Allylated
Sen Yang1, Zhuo Chen1, Sha-Sha Cai1
1Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou213164, China.
Abstract:
An efficient tandem amidyl-radical cyclization/alkyl radical Heck reaction for the construction of allylated γ-lactams has been developed under visible-light-induced palladium catalysis. The reaction proceeds via an amidyl radical/Pd(I) hybrid species generated through photoexcited Pd(0)-mediated N-O bond cleavage of N-acyloxyamides, followed by intramolecular cyclization to form an alkyl-Pd(I) intermediate. This intermediate subsequently undergoes an intermolecular alkyl radical Heck reaction with vinyl arenes, furnishing N-alkyl allylated γ-lactams bearing diverse functional groups under mild conditions. Furthermore, successful late-stage functionalization of bioactive molecules and downstream transformations of the products underscore the utility of this method.
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