{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Lei Z"],"funding":["NIGMS NIH HHS"],"pagination":["7318-7323"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC6527503"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["58(22)"],"pubmed_abstract":["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."],"journal":["Angewandte Chemie (International ed. in English)"],"pubmed_title":["?-Selective Aroylation of Activated Alkenes by Photoredox Catalysis."],"pmcid":["PMC6527503"],"funding_grant_id":["R35 GM128779","R35 GM119652"],"pubmed_authors":["Rizzo E","Lei Z","Liu P","Ngai MY","Kusevska E","Banerjee A"],"additional_accession":[]},"is_claimable":false,"name":"?-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.","description":"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.","dates":{"release":"2019-01-01T00:00:00Z","publication":"2019 May","modification":"2020-10-29T13:52:26Z","creation":"2020-05-30T07:02:27Z"},"accession":"S-EPMC6527503","cross_references":{"pubmed":["30994977"],"doi":["10.1002/anie.201901874"]}}