Jump to main content
Jump to site search


Buchwald–Hartwig cross-coupling of amides (transamidation) by selective N–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts: catalyst evaluation and mechanism

Author affiliations

Abstract

The Pd–NHC-catalyzed acyl-type Buchwald–Hartwig cross-coupling of amides by N–C(O) cleavage (transamidation) provides a valuable alternative to the classical methods for amide synthesis. Herein, we report a combined experimental and computational study of the Buchwald–Hartwig cross-coupling of amides using well-defined, air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts. Most crucially, we present a comprehensive evaluation of a series of distinct Pd(II)–NHC precatalysts featuring different NHC scaffolds and throw-away ligands for the synthesis of functionalized amides that are not compatible with stoichiometric transition-metal-free transamidation methods. Furthermore, we present evaluation of the catalytic cycle by DFT methods for a series of different Pd(II)–NHC precatalysts. The viability of accessing NHC-supported acyl-palladium(II) amido complexes will have implications for the design and development of cross-coupling methods involving stable amide electrophiles.

Graphical abstract: Buchwald–Hartwig cross-coupling of amides (transamidation) by selective N–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts: catalyst evaluation and mechanism

Back to tab navigation

Supplementary files

Article information


Submitted
15 Oct 2019
Accepted
20 Dec 2019
First published
23 Dec 2019

Catal. Sci. Technol., 2020, Advance Article
Article type
Paper

Buchwald–Hartwig cross-coupling of amides (transamidation) by selective N–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts: catalyst evaluation and mechanism

G. Li, T. Zhou, A. Poater, L. Cavallo, S. P. Nolan and M. Szostak, Catal. Sci. Technol., 2020, Advance Article , DOI: 10.1039/C9CY02080B

Social activity

Search articles by author

Spotlight

Advertisements