Back to Search
Start Over
β-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2019 May 27; Vol. 58 (22), pp. 7318-7323. Date of Electronic Publication: 2019 Apr 17. - Publication Year :
- 2019
-
Abstract
- 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.<br /> (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 58
- Issue :
- 22
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 30994977
- Full Text :
- https://doi.org/10.1002/anie.201901874