Versatile and Highly Efficient trans-[Pd(NHC)Cl2(DMS/THT)] Precatalysts for C-N and C-C Coupling Reactions in Green Solvents

被引：13

作者：

Liu, Yaxu ^{[1
,2
]}

Voloshkin, Vladislav A. ^{[1
,2
]}

Scattolin, Thomas ^{[3
]}

Peng, Min ^{[1
,2
]}

Van Hecke, Kristof ^{[1
,2
]}

Nolan, Steven P. ^{[1
,2
]}

Cazin, Catherine S. J. ^{[1
,2
]}

机构：

[1] Univ Ghent, Dept Chem, Krijgslaan 281,S-3, B-9000 Ghent, Belgium

[2] Univ Ghent, Ctr Sustainable Chem, Krijgslaan 281,S-3, B-9000 Ghent, Belgium

[3] Univ Padua, Dipartimento Sci Chim, Via Marzolo 1, I-35131 Padua, Italy

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2022年 / 2022卷 / 14期

基金：

比利时弗兰德研究基金会;

关键词：

Buchwald-Hartwig amination; cross-coupling; N-Heterocyclic carbenes; Palladium; BUCHWALD-HARTWIG AMINATION; HETEROCYCLIC CARBENE COMPLEXES; PD-PEPPSI-IPENT; SUZUKI-MIYAURA; PALLADIUM COMPLEXES; ROOM-TEMPERATURE; NHC NHC; (NHC)PD(ALLYL)CL NHC; OXIDATIVE ADDITION; CATALYTIC-ACTIVITY;

D O I：

10.1002/ejoc.202200309

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A straightforward synthetic procedure to well-defined, air- and moisture- stable trans-[Pd(NHC)Cl-2(DMS/THT)] (NHC-IPr, SIPr, IMes, IPrCl,IPr*,IPr#) pre-catalysts is reported. These complexes were obtained by reacting NHC center dot HCl imidazolium salts with trans-[PdCl2(DMS/THT)(2)] precursors with the assistance of the weak base K2CO3 in green acetone at 40 degrees C. The scalability of this protocol was demonstrated. The catalytic activity of the synthesized complexes was studied in the Buchwald-Hartwig and Suzuki-Miyaura reactions. Remarkably, most of the synthesized complexes exhibit higher catalytic activity with respect to their PEPPSI congeners in the Buchwald-Hartwig amination 2-MeTHF. In particular, complex trans-[Pd(IPr#)Cl-2(DMS)] enabled the coupling of various (hetero)aryl chlorides and primary/secondary amines with a 0.2 mol% catalyst loading. In addition, trans-[Pd(IPOCI,(DMS)] showed excellent performance in the room-temperature Suzuki-Miyaura reaction involving various (hetero)aryl chlorides and aryl boronic acids. In summary, the synthesized complexes, especially trans-[Pd(NHC)Cl-2(DMS)], can be considered as greener alternatives to classical PEPPSI type catalysts based on the lower toxicity of the throw-away DMS ligand compared to 3-chloropyridine.

引用

页数：12

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