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单核八面体钌(II)配合物实现了具有可移除辅助基团的芳环间位 C-H 硝化反应。

Monomeric Octahedral Ruthenium(II) Complex Enabled meta-C-H Nitration of Arenes with Removable Auxiliaries.

机构信息

CAS Key Laboratory of Receptor Research and the State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica (SIMM), Chinese Academy of Sciences , Shanghai 201203, China.

University of Chinese Academy of Sciences , Beijing 100049, China.

出版信息

Org Lett. 2017 Jun 16;19(12):3199-3202. doi: 10.1021/acs.orglett.7b01297. Epub 2017 Jun 2.

Abstract

A removable oxime-assisted meta-C-H nitration of arenes is reported. Mechanistic investigations and DFT calculations reveal a new monomeric octahedral ruthenium(II) complex is responsible for the meta-selective nitration. Dioxygen as a cooxidant is crucial for achieving high conversion and good yields. Moreover, the utility of the present reaction protocol is further showcased by the late-stage modification of the clinical CNS drugs Diazepam and Fluvoxamine.

摘要

报道了一种可去除肟辅助的芳烃间位 C-H 硝化反应。通过机理研究和 DFT 计算揭示了一种新型单核八面体钌(II)配合物是导致间位选择性硝化的原因。氧气作为共氧化剂对于实现高转化率和良好收率至关重要。此外,本反应方案的实用性还通过对临床 CNS 药物地西泮和氟伏沙明的后期修饰得到了进一步展示。

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