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Hydrogen-Bonded Electron Donor-Acceptor Complex Enables Markovnikov Hydroarylation and Hydroxyalkylation of N-Acyl
Zhenda Su1, Tingtao Yan1, Kelu Yan1
1Key Laboratory of Green Natural Products and Pharmaceutical Intermediates in Colleges and Universities of Shandong Province, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu273165, Shandong, China.
Abstract:
Visible-light-mediated electron donor-acceptor (EDA) complex catalysis has emerged as a powerful strategy for radical transformations under mild conditions, yet EDA donor catalytic systems driven by hydrogen bonding remain largely underexplored. Herein, we report a H-bonded EDA (H-EDA) donor catalysis system, employing thiols as donor catalysts to achieve Markovnikov hydroarylation and hydroxyalkylation of N-acyl enamines under redox-neutral conditions. This protocol proceeds under metal-free, base-free, and redox auxiliary-free conditions with complete atom economy. Mechanistic studies reveal that the reaction proceeds through oxidative nucleophilic coupling enabled by a photoinduced H-EDA complex via SET and 1,5-H-shift. The protocol features broad substrate scope, excellent regioselectivity, and gram-scale scalability. This work establishes a general H-EDA donor catalytic platform and redefines EDA donor catalysis beyond conventional redox auxiliary (RA)-mediated activation.
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