Radical-mediated Ester Group Migration for 1,2,3-Trifunctionalization of Allyl Benzoates

doi:10.1007/s40242-025-5146-1

Chemical Research in Chinese Universities ›› 2026, Vol. 42 ›› Issue (1): 212-222.doi: 10.1007/s40242-025-5146-1

• Research Articles • Previous Articles Next Articles

Radical-mediated Ester Group Migration for 1,2,3-Trifunctionalization of Allyl Benzoates

WANG Ziqiang^1,2, SHAO Xin², CHEN Yasu¹, ZHU Chen^1,2

1. Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai 200240, P. R. China;
2. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China

Received:2025-07-13 Online:2026-02-01 Published:2026-01-28
Contact: ZHU Chen,E-mail:chzhu@sjtu.edu.cn E-mail:chzhu@sjtu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 22371185, 22171201), the Fundamental Research Funds for the Central Universities, China (Nos. 23X010301599, 24X010301678), and the Program of Shanghai Academic/Technology Research Leader, China (No. 23XD1421900).

Abstract

Abstract: Unactivated alkenes are normally regarded as unfavorable substrates in radical transformations, due to the lack of p-π conjugation that efficiently stabilizes radical intermediates. Functional group migration presents a robust strategy for radical difunctionalization of unactivated alkenes, and has made a great progress over the past few decades. However, the migration of ester group has been relatively less investigated. Herein, we disclose a copper-catalyzed ester group migration to unactivated alkene, applied for 1,2,3-trifunctionalization of allyl benzoates. A variety of α,α-difluoro-γ-hydroxy aliphatic esters are readily obtained.

Key words: Radical reaction, Functional group migration, Ester migration, Alkene functionalization, Copper catalysis

WANG Ziqiang, SHAO Xin, CHEN Yasu, ZHU Chen. Radical-mediated Ester Group Migration for 1,2,3-Trifunctionalization of Allyl Benzoates[J]. Chemical Research in Chinese Universities, 2026, 42(1): 212-222.

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Radical-mediated Ester Group Migration for 1,2,3-Trifunctionalization of Allyl Benzoates

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