Native Amide-Directed C(sp3 )-H Amidation Enabled by Electron-Deficient RhIII Catalyst and Electron-Deficient 2-Pyridone Ligand

Takumi Wakikawa; Daichi Sekine; Yuta Murata; Youka Bunno; Masahiro Kojima; Yuki Nagashima; Ken Tanaka; Tatsuhiko Yoshino; Shigeki Matsunaga

doi:10.1002/anie.202213659

Native Amide-Directed C(sp³ )-H Amidation Enabled by Electron-Deficient Rh^III Catalyst and Electron-Deficient 2-Pyridone Ligand

Angew Chem Int Ed Engl. 2022 Dec 23;61(52):e202213659. doi: 10.1002/anie.202213659. Epub 2022 Nov 23.

Authors

Affiliations

¹ Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo, 060-0812, Japan.
² Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
³ Global Station for Biosurfaces and Drug Discovery, Hokkaido University, Kita-ku, Sapporo, 060-0812, Japan.

PMID: 36305194
DOI: 10.1002/anie.202213659

Abstract

Trivalent group-9 metal catalysts with a cyclopentadienyl-type ligand (CpM^III ; M=Co, Rh, Ir, Cp=cyclopentadienyl) have been widely used for directed C-H functionalizations, albeit that their application to challenging C(sp³ )-H functionalizations suffers from the limitations of the available directing groups. In this report, we describe directed C(sp³ )-H amidation reactions of simple amide substrates with a variety of substituents. The combination of an electron-deficient Cp^E Rh catalyst (Cp^E =1,3-bis(ethoxycarbonyl)-substituted Cp) and an electron-deficient 2-pyridone ligand is essential for high reactivity.

Keywords: 2-Pyridone; Amide; C−H Activation; Dioxazolone; Rhodium.

Abstract

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