Cross-Coupling of Amides by N–C Bond Activation

^‡ These authors contributed equally.

Abstract

In recent years, significant conceptual advances have taken place in the field of amide bond cross-coupling. Mild and selective functionalization of amides by transition-metal catalysis has an enormous potential for widespread applications in both industry and academia due to the unparalleled prevalence of amide-containing molecules. However, direct metal insertion into the N–C(O) amide bond is extremely difficult as a consequence of amidic resonance. In this account, we summarize our work on the development of new cross-coupling reactions of amides by N–C bond activation, and briefly discuss other modern developments in this area.

1 Introduction

2 Amide Bond Ground-State Distortion

3 Acyl Amide N–C Cross-Coupling

3.1 Suzuki Cross-Coupling

3.2 Negishi Cross-Coupling

3.3 Esterification and Amidation via N–C Cross-Coupling

4 Decarbonylative Amide N–C Cross-Coupling

4.1 Heck Cross-Coupling

4.2 Suzuki Cross-Coupling

4.3 C–H Activation

4.4 Decarbonylative Borylation

5 Transition-Metal-Free Activation of Amide Bonds

6 Mechanistic Studies

7 Conclusions and Outlook

Key words

amides - cross-coupling - N–C bond activation - Suzuki coupling - decarbonylative coupling - C–H activation - palladium - nickel

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