biostudies-literatureLei ZNIGMS NIH HHS7318-7323https://www.ebi.ac.uk/biostudies/studies/S-EPMC6527503biostudies-literatureUnknown58(22)Late-stage synthesis of ?,?-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 ?-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 ?-chloro-?-hydroxy benzyl radical, and 1,3-chlorine atom shift.Angewandte Chemie (International ed. in English)?-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.PMC6527503R35 GM128779R35 GM119652Rizzo ELei ZLiu PNgai MYKusevska EBanerjee Afalse?-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.Late-stage synthesis of ?,?-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 ?-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 ?-chloro-?-hydroxy benzyl radical, and 1,3-chlorine atom shift.2019-01-01T00:00:00Z2019 May2020-10-29T13:52:26Z2020-05-30T07:02:27ZS-EPMC65275033099497710.1002/anie.201901874