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6940875 
Journal Article 
β-Selective Aroylation of Activated Alkenes by Photoredox Catalysis 
Lei, Z; Banerjee, A; Kusevska, E; Rizzo, E; Liu, P; Ngai, MY; , 
2019 
Yes 
Angewandte Chemie (International Edition)
ISSN: 1433-7851
EISSN: 1521-3773 
English 
30994977 
Late-stage synthesis of α,β-unsaturated aryl ketones remains an unmet challenge in organic synthesis. Reported herein is a photocatalytic non-chain-radical aroyl chlorination of alkenes by a 1,3-chlorine atom shift to form β-chloroketones as masked enones that liberate the desired enones upon workup. This strategy suppresses side reactions of the enone products. The reaction tolerates a wide array of functional groups and complex molecules including derivatives of peptides, sugars, natural products, nucleosides, and marketed drugs. Notably, addition of 2,6-di-tert-butyl-4-methyl-pyridine enhances the quantum yield and efficiency of the cross-coupling reaction. Experimental and computational studies suggest a mechanism involving PCET, formation and reaction of an α-chloro-α-hydroxy benzyl radical, and 1,3-chlorine atom shift.