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Synthesis 2018; 50(15): 3015-3021
DOI: 10.1055/s-0037-1609964
DOI: 10.1055/s-0037-1609964
special topic
Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams
This work was supported by Grants-in-Aid for Scientific Research (A) (no. 26248031) from JSPS and Scientific Research on Innovative Areas 2707 Middle molecular strategy (no. 15H05850) from MEXT.Further Information
Publication History
Received: 07 March 2018
Accepted after revision: 18 April 2018
Publication Date:
29 May 2018 (online)
Published as part of the Special Topic Modern Radical Methods and their Strategic Applications in Synthesis
Abstract
A metal-catalyst-free intramolecular Heck carbonylation reaction of benzyl alcohols and benzyl amines with carbon monoxide under heating at 250 °C affords the corresponding benzolactones and benzolactams in good to excellent yields. A hybrid radical/ionic chain mechanism, involving electron transfer from radical anions generated by nucleophilic attack of alcohols or amines on intermediate acyl radicals, is proposed.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1609964.
- Supporting Information
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For reviews on radical carbonylation, see:
For reviews, see:
For carbonylative synthesis of amides and lactams including trapping of acyl radicals by amines, see: