Thioamide directed Co(III) catalyzed selective amidation of C(sp3)-H bonds

Journal article

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 via 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/quinolone classes for Cp*CoIII catalyzed C(sp3)-H functionalization and the first to exploit thioamides.

Authors: Tan, P; Mak, A; Sullivan, M; Dixon, D; Seayad, J

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Wiley
• Journal: Angewandte Chemie International Edition
• Volume: 56
• Issue: 52
• Pages: 16550–16554
• Publication date: 2017-11-30
• Acceptance date: 2017-10-24
• DOI: 10.1002/anie.201709273
• EISSN: 1521-3773
• ISSN: 1433-7851
• Pmid: 29080308
• Language: English
• Keywords: amidation; thioamide; cobalt Cp*; selective; C(sp3)-H activation