Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 22, Pages 7318-7323Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201901874
Keywords
alkenes; aroylation; photochemistry; radicals; synthetic methods
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Funding
- National Institute of General Medical Sciences [R35GM119652, R35GM128779]
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Late-stage synthesis of alpha,beta -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 beta -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 alpha -chloro-alpha -hydroxy benzyl radical, and 1,3-chlorine atom shift.
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