Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Nitrosonium-Mediated Phenol–Arene Cross-Coupling Involving Direct C–H Activation

Anna Eisenhofer A , Uta Wille B C and Burkhard König A C
+ Author Affiliations
- Author Affiliations

A Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg, D-93040 Regensburg, Germany.

B School of Chemistry, Bio21 Institute, The University of Melbourne, 30 Flemington Road, Parkville, Vic. 3010, Australia.

C Corresponding authors. Email: uwille@unimelb.edu.au; burkhard.koenig@ur.de

Australian Journal of Chemistry 70(4) 407-412 https://doi.org/10.1071/CH16622
Submitted: 3 November 2016  Accepted: 15 December 2016   Published: 6 February 2017

Abstract

The nitrosonium ion (NO+) is a highly versatile nitration and nitrosation reagent, as well as a strong one-electron oxidant. Herein, we describe an environmentally benign and mild method for the in situ formation of NO+ from readily available inorganic nitrate salts, i.e. lithium nitrate, through a finely tuned interplay between formic acid and MeOH, which are used as the solvent system. This methodology was applied to the NO+-induced oxidative C–H activation of methoxy-substituted phenols, which are versatile lignin-derived aromatic feedstocks, to achieve C–C cross-coupling reactions with arenes. The regeneration of NO+ by atmospheric molecular oxygen enables substoichiometric use of the nitrate.


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