Synthesis 2018; 50(15): 3015-3021
DOI: 10.1055/s-0037-1609964
special topic
© Georg Thieme Verlag Stuttgart · New York

Electron-Transfer-Induced Intramolecular Heck Carbonylation Reactions Leading to Benzolactones and Benzolactams

Takahide Fukuyama
a   Department of Chemistry, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka, 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
,
Takanobu Bando
a   Department of Chemistry, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka, 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
,
Ilhyong Ryu*
a   Department of Chemistry, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka, 599-8531, Japan   Email: ryu@c.s.osakafu-u.ac.jp
b   Department of Applied Chemistry, National Chiao Tung University, 1001 University Road, Hsinchu, Taiwan
› Author Affiliations
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

 
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