期刊
CATALYSIS SCIENCE & TECHNOLOGY
卷 11, 期 9, 页码 3189-3197出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cy00312g
关键词
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资金
- Rutgers University
- NSF [CHE-1650766]
- NIH [1R35GM133326]
- Rutgers University - Newark Chancellor's Research Office
- NSF-MRI grant [CHE-1229030]
- Spanish MINECO [PGC2018-097722-B-I00]
- European Fund for Regional Development (FEDER) [UNGI10-4E-801]
- BOF
- SBO projects
The study presents a new Pd(ii)-NHC precatalyst for the Suzuki-Miyaura cross-coupling of aryl esters, demonstrating it to be the most reactive precatalyst discovered so far in this reactivity manifold. The unconventional O-C(O) cross-coupling reaction is highlighted for its unique synthetic utility in late-stage functionalization of pharmaceuticals and sequential chemoselective coupling.
The cross-coupling of aryl esters has emerged as a powerful platform for the functionalization of otherwise inert acyl C-O bonds in chemical synthesis and catalysis. Herein, we report a combined experimental and computational study on the acyl Suzuki-Miyaura cross-coupling of aryl esters mediated by well-defined, air- and moisture-stable Pd(ii)-NHC precatalysts [Pd(NHC)(mu-Cl)Cl](2). We present a comprehensive evaluation of [Pd(NHC)(mu-Cl)Cl](2) precatalysts and compare them with the present state-of-the-art [(Pd(NHC)allyl] precatalysts bearing allyl-type throw-away ligands. Most importantly, the study reveals [Pd(NHC)(mu-Cl)Cl](2) as the most reactive precatalysts discovered to date in this reactivity manifold. The unique synthetic utility of this unconventional O-C(O) cross-coupling is highlighted in the late-stage functionalization of pharmaceuticals and sequential chemoselective cross-coupling, providing access to valuable ketone products by a catalytic mechanism involving Pd insertion into the aryl ester bond. Furthermore, we present a comprehensive study of the catalytic cycle by DFT methods. Considering the clear advantages of [Pd(NHC)(mu-Cl)Cl](2) precatalysts on several levels, including facile one-pot synthesis, superior atom-economic profile to all other Pd(ii)-NHC catalysts, and versatile reactivity, these should be considered as the 'first-choice' catalysts for all routine applications in ester O-C(O) bond activation.
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