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Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3 )-H Bonds
Peng Wen Tan1, Adrian M Mak2, Michael B Sullivan2
1Organic Chemistry, Institute of Chemical and Engineering Sciences, 8 Biomedical Grove, Neuros, #07-01, Singapore, 138665, Singapore.
Abstract:
A mild, oxidant-free, and selective Cp*CoIII -catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3 )-H bond activation to generate the desired amidated products is reported. The method is efficient and allows for the C-H amidation of a wide range of functionalized thioamides with aryl-, heteroaryl-, and alkyl-substituted dioxazolones under the Cp*CoIII -catalyzed conditions. The observed regioselectivity towards primary C(sp3 )-H activation is supported by computational studies and the cyclometalation is proposed to proceed by means of an external carboxylate-assisted concerted metalation/deprotonation mechanism. The reported method is a rare example of the use of a directing group other than the commonly used pyridine and quinolone classes for Cp*CoIII -catalyzed C(sp3 )-H functionalization and the first to exploit thioamides.
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