2016年6月15日水曜日

Meta-Selective CAr–H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy - Journal of the American Chemical Society (ACS Publications)

Meta-Selective CAr–H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy - Journal of the American Chemical Society (ACS Publications)

Zhoulong Fan, Jiabin Ni, and Ao Zhang*
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., Article ASAP
DOI: 10.1021/jacs.6b03402
Publication Date (Web): May 15, 2016
Copyright © 2016 American Chemical Society

Abstract

Abstract Image
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.

0 件のコメント:

コメントを投稿