Issue 2, 2016

Nickel-catalyzed trifluoromethylthiolation of Csp2–O bonds


While nickel catalysts have previously been shown to activate even the least reactive Csp2–O bonds, i.e. aryl ethers, in the context of C–C bond formation, little is known about the reactivity limits and molecular requirements for the introduction of valuable functional groups under homogeneous nickel catalysis. We identified that due to the high reactivity of Ni-catalysts, they are also prone to react with existing or installed functional groups, which ultimately causes catalyst deactivation. The scope of the Ni-catalyzed coupling protocol will therefore be dictated by the reactivity of the functional groups towards the catalyst. Herein, we showed that the application of computational tools allowed the identification of matching functional groups in terms of suitable leaving groups and tolerated functional groups. This allowed for the development of the first efficient protocol to trifluoromethylthiolate Csp2–O bonds, giving the mild and operationally simple C–SCF3 coupling of a range of aryl, vinyl triflates and nonaflates. The novel methodology was also applied to biologically active and pharmaceutical relevant targets, showcasing its robustness and wide applicability.

Graphical abstract: Nickel-catalyzed trifluoromethylthiolation of Csp2–O bonds

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Article information

Article type
Edge Article
06 Sep 2015
30 Oct 2015
First published
30 Oct 2015
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., 2016,7, 1076-1081

Nickel-catalyzed trifluoromethylthiolation of Csp2–O bonds

A. B. Dürr, G. Yin, I. Kalvet, F. Napoly and F. Schoenebeck, Chem. Sci., 2016, 7, 1076 DOI: 10.1039/C5SC03359D

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