Meta-Selective CAr–H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy
† CAS Key Laboratory of Receptor Research, and Synthetic Organic & Medicinal Chemistry Laboratory (SOMCL), Shanghai Institute of Materia Medica (SIMM), Chinese Academy of Sciences, Shanghai 201203, China
‡ University of Chinese Academy of Sciences, Beijing 100049, China
J. Am. Chem. Soc., 2016, 138 (27), pp 8470–8475
DOI: 10.1021/jacs.6b03402
Publication Date (Web): May 15, 2016
Copyright © 2016 American Chemical Society
Abstract
The first example of transition metal-catalyzed meta-selective CAr–H nitration of arenes is described. With the use of Ru3(CO)12 as the catalyst and Cu(NO3)2·3H2O as the nitro source, a wide spectrum of arenes bearing diversified N-heterocycles or oximido as the directing groups were nitrated with meta-selectivity exclusively.
Mechanism studies have demonstrated the formation of a new 18e-octahedral ruthenium species as a key ortho-CAr–H metalated intermediate, which may be responsible for the subsequent meta-selective electrophilic aromatic substitution (SEAr).
Moreover, this approach provides a fast-track strategy for atom/step economical synthesis of many useful pharmaceutical molecules.
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b03402.
- Experimental procedures, characterization data, and 1H and 13C NMR spectra for all new compounds (PDF)
- X-ray for complex A (CCDC 1456692) (CIF)
Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.
- Hang Shi
, Peng Wang, Shin Suzuki, Marcus E. Farmer, and Jin-Quan YuJournal of the American Chemical Society 2016 Article ASAP - Jiabin Ni
, Jie Li, Zhoulong Fan, and Ao ZhangOrganic Letters 2016 Article ASAP - Michael J. Lopez
, Ai Kondo, Haruki Nagae, Koji Yamamoto, Hayato Tsurugi, and Kazushi MashimaOrganometallics 2016 Article ASAP - Peng Wang
, Gen-Cheng Li, Pankaj Jain, Marcus E. Farmer, Jian He, Peng-Xiang Shen, and Jin-Quan YuJournal of the American Chemical Society 2016 138 (42), 14092-14099 - Mingchun Gao
and Bin XuOrganic Letters 2016 18 (18), 4746-4749 
Mingchun Gaoand Bin XuOrganic Letters 2016 18 (18), 4746-4749AgNO 3 as nitrogen source for rhodium( iii )-catalyzed synthesis of 2-aryl-2H-benzotriazoles from azobenzenes
Jixing Li, Hui Zhou, Jinlong Zhang, Huameng Yang, Gaoxi JiangChem. Commun. 2016 ,
0 件のコメント:
コメントを投稿