Abstract
In the past several years, tremendous advances have been made in non-classical routes
for amide bond formation that involve transamidation and amidation reactions of activated
amides and esters. These new methods enable the formation of extremely valuable amide
bonds via transition-metal-catalyzed, transition-metal-free, or metal-free pathways
by exploiting chemoselective acyl C–X (X = N, O) cleavage under mild conditions. In
a broadest sense, these reactions overcome the formidable challenge of activating
C–N/C–O bonds of amides or esters by rationally tackling nN → π*C=O delocalization in amides and nO → π*C=O donation in esters. In this account, we summarize the recent remarkable advances
in the development of new methods for the synthesis of amides with a focus on (1)
transition-metal/NHC-catalyzed C–N/C–O bond activation, (2) transition-metal-free
highly selective cleavage of C–N/C–O bonds, (3) the development of new acyl-transfer
reagents, and (4) other emerging methods.
1 Introduction
2 Transamidation of Amides
2.1 Transamidation by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)
2.2 Transition-Metal-Free Transamidation via Tetrahedral Intermediates
2.3 Reductive Transamidation
2.4 New Acyl-Transfer Reagents
2.5 Tandem Transamidations
3 Amidation of Esters
3.1 Amidation of Esters by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)
3.2 Transition-Metal-Free Amidation of Esters via Tetrahedral Intermediates
3.3 Reductive Amidation of Esters
4 Transamidations of Amides by Other Mechanisms
5 Conclusions and Outlook
Key words
amides - transamidation - esters - amidation - transition-metal-free - palladium -
nickel
