Wydział Chemii

Chang-An Wang

Md. Mahbubur Rahman

Elwira Bisz

Błażej Dziuk

Roman Szostak

Michal Szostak

2022

ACS Catalysis

12

2426-2433

10.1021/acscatal.1c05738

Naukowa

Angielski

Artykuł

We report the Pd-catalyzed Suzuki–Miyaura cross-coupling of aliphatic amides. Although tremendous advances have been made in the cross-coupling of aromatic amides, C–C bond formation from aliphatic amides by selective N–C(O) cleavage has remained a major challenge. This longstanding problem in Pd catalysis has been addressed herein by a combination of (1) the discovery of N,N-pym/Boc amides as a class of readily accessible amide-based reagents for cross-coupling and (2) steric tuning of well-defined Pd(II)-NHC catalysts for cross-coupling. The methodology is effective for the cross-coupling of an array of 3°, 2°, and 1° aliphatic amide derivatives. The catalyst system is user-friendly, since the catalysts are readily available and are air- and bench-stable. Mechanistic studies strongly support an amide bond twist and external n_N → π*_C═O/Ar delocalization as a unified enabling feature of N,N-pym/Boc amides in selective N–C(O) bond activation. The method provides a rare example of Pd-NHC-catalyzed cross-coupling of aliphatic acyl amide electrophiles.

cross-coupling, Pd-NHCs, N−C activation, alkyl amides, amide resonance, twisted amides

http://dx.doi.org/10.1021/acscatal.1c05738

https://www.acs.org/content/acs/en.html