Regioselective C-H thioarylation of electron-rich arenes by iron(III) triflimide catalysis

Dodds, A. C. and Sutherland, A. (2021) Regioselective C-H thioarylation of electron-rich arenes by iron(III) triflimide catalysis. Journal of Organic Chemistry, 86(8), pp. 5922-5932. (doi: 10.1021/acs.joc.1c00448) (PMID:33783222)

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Abstract

A mild and regioselective method for the preparation of unsymmetrical biaryl sulfides using iron(III) catalysis is described. Activation of N-(arylthio)succinimides using the powerful Lewis acid iron(III) triflimide allowed the efficient thiolation of a range of arenes, including anisoles, phenols, acetanilides, and N-heterocycles. The method was applicable for the late-stage thiolation of tyrosine and tryptophan derivatives and was used as the key step for the synthesis of pharmaceutically relevant biaryl sulfur-containing compounds such as the antibiotic dapsone and the antidepressant vortioxetine. Kinetic studies revealed that while N-(arylthio)succinimides bearing electron-deficient arenes underwent thioarylation catalyzed entirely by iron(III) triflimide, N-(arylthio)succinimides with electron-rich arenes displayed an autocatalytic mechanism promoted by the Lewis basic product.

Item Type:Articles
Additional Information:Financial support from The Carnegie Trust for the Universities of Scotland (Ph.D. studentship to A.C.D.) and the University of Glasgow is gratefully acknowledged.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Dodds, Amy and Sutherland, Professor Andrew
Authors: Dodds, A. C., and Sutherland, A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Organic Chemistry
Publisher:American Chemical Society
ISSN:0022-3263
ISSN (Online):1520-6904
Published Online:30 March 2021
Copyright Holders:Copyright © 2021 American Chemical Society
First Published:First published in Journal of Organic Chemistry 86(8): 5922-5932
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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