Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Org Lett. 2010 Sep 17;12(18):4195-7. doi: 10.1021/ol1018079.
The direct oxidation of ether sp(3) C-H bonds using the new reagent system mCPBA/CCl(3)CN/MeCN has been developed. CCl(3)CN in MeCN drastically alters the reactivity of m-chloroperbenzoic acid (mCPBA), and chemoselective transformation of methyl ethers to ketones was realized under mild conditions. Radical-based mCPBA-mediated oxidation was suggested as the reaction mechanism. The present new reaction expands the utility of methyl ethers as stable synthetic precursors of carbonyl compounds and of mCPBA as a radical-based C-H oxidizing agent.
已开发出使用新型试剂体系 mCPBA/CCl(3)CN/MeCN 直接氧化醚 sp(3) C-H 键的方法。MeCN 中的 CCl(3)CN 极大地改变了间氯过氧苯甲酸 (mCPBA) 的反应活性，并且在温和条件下实现了甲基醚的选择性转化为酮。基于自由基的 mCPBA 介导的氧化被认为是反应机制。本新反应扩展了甲基醚作为羰基化合物的稳定合成前体以及 mCPBA 作为基于自由基的 C-H 氧化剂的用途。
