Aerobic Oxidation of PMB Ethers to Carboxylic Acids

Author:

Zhang Qian1,Zhang Jiabin2,Qian Hui1,Ma Shengming123ORCID

Affiliation:

1. Research Center for Molecular Recognition and Synthesis Department of Chemistry Fudan University 220 Handan Lu Shanghai 200433 China

2. Laboratory of Molecular Recognition and Synthesis Department of Chemistry Zhejiang University Hangzhou 310027, Zhejiang Province China

3. State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China

Abstract

AbstractThe first aerobic protocol of direct transformation of p‐methoxybenzyl (PMB) ethers to carboxylic acids efficiently with Fe(NO3)3 ⋅ 9H2O and TEMPO as catalysts at room temperature has been developed. The reaction accommodates C−Br bond, terminal/non‐terminal C−C triple bond, amide, cyano, nitro, ester, and trifluoromethyl groups. Even highly selective oxidative deprotection of different benzylic PMB ethers has been realized. The reaction has been successfully applied to the total synthesis of natural product, (R)‐6‐hydroxy‐7,9‐octadecadiynoic acid, demonstrating the practicality of the method. Based on experimental studies, a possible mechanism involving oxygen‐stabilized benzylic cation has been proposed.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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