Issue 1, 2017

Unified synthesis of mono/bis-arylated phenols via RhIII-catalyzed dehydrogenative coupling

Abstract

2,6-Bis-arylated phenols are rarely reported and are synthetically challenging. Directed C–H functionalization reactions, using a directing group (DG), might provide a convenient solution to their synthesis. However, this strategy usually results in partial cleavage of the directing group, preventing further/second C–H activation cascades. Herein we report a general strategy that allows for the precise control of the oxidation pathways so that directing groups can be either preserved or cleaved. We found that N-phenoxyacetamides could undergo ortho-arylation reactions with or without an external oxidant, yielding products with different oxidation states, notably the rare bis-arylated phenols. Notably, a unique rhodacycle intermediate was isolated, characterized by X-ray crystallography, and confirmed to be an active catalyst. Switching between internal and external oxidation could be a general strategy in diverse directed C–H functionalization reactions to realize bis-functionalized products.

Graphical abstract: Unified synthesis of mono/bis-arylated phenols via RhIII-catalyzed dehydrogenative coupling

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Jul 2016
Accepted
02 Aug 2016
First published
03 Aug 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 169-173

Unified synthesis of mono/bis-arylated phenols via RhIII-catalyzed dehydrogenative coupling

Q. Wu, Y. Chen, D. Yan, M. Zhang, Y. Lu, W. Sun and J. Zhao, Chem. Sci., 2017, 8, 169 DOI: 10.1039/C6SC03169B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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