Chemoselective Oxyfunctionalization of Functionalized Benzylic Compounds with a Manganese Catalyst

• Type of Material: Article
• Authors: Jimei Zhou, Shaanxi Normal University; Jun Zhou, Emory University; Minxian Jia, Shaanxi Normal University; Menghui Song, Shaanxi Normal University; Zhiliang Huang, University of Liverpool; Alexander Steiner, University of Liverpool; Qidong An, Shaanxi Normal University; Jianwei Ma, Shaanxi Normal University; Zhiyin Guo, Shaanxi Normal University; Qianqian Zhang, Shaanxi Normal University; Huaming Sun, Shaanxi Normal University; Craig Robertson, University of Liverpool; John Bacsa, Emory University; Jianliang Xiao, University of Liverpool; Chaoqun Li, Shaanxi Normal University
• Language: English
• Date: 2022-07-25
• Publisher: Wiley-VCH GmbH
• Publication Version: Final Published Version
• Copyright Statement: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
• License: Creative Commons Attribution 4.0 International
• Final Published Version (URL): http://dx.doi.org/10.1002/anie.202205983
• Title of Journal or Parent Work: Angewandte Chemie - International Edition
• Volume: 61
• Issue: 30
• Start Page: e202205983
• End Page: e202205983
• Keywords: Manganese Catalysts; Cyclic Imines; Manganese; Alkynes; Ions; Benzylic Oxidation; Selective Oxidation; Catalysis; Oxidation-Reduction; Ketones
• Research Categories: Chemistry, General

Abstract

Whilst allowing for easy access to synthetically versatile motifs and for modification of bioactive molecules, the chemoselective benzylic oxidation reactions of functionalized alkyl arenes remain challenging. Reported in this study is a new non-heme Mn catalyst stabilized by a bipiperidine-based tetradentate ligand, which enables methylene oxidation of benzylic compounds by H2O2, showing high activity and excellent chemoselectivity under mild conditions. The protocol tolerates an unprecedentedly wide range of functional groups, including carboxylic acid and derivatives, ketone, cyano, azide, acetate, sulfonate, alkyne, amino acid, and amine units, thus providing a low-cost, more sustainable and robust pathway for the facile synthesis of ketones, increase of complexity of organic molecules, and late-stage modification of drugs.