Xia Qinqin, Shi Shicheng, Gao Pengcheng, Lalancette Roger, Szostak Roman, Szostak Michal
School of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou 325035, China.
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States.
J Org Chem. 2021 Nov 5;86(21):15648-15657. doi: 10.1021/acs.joc.1c02183. Epub 2021 Oct 7.
We report the synthesis, characterization, and reactivity of [(NHC)PdCl(aniline)] complexes. These well-defined, air- and moisture-stable catalysts are highly active in the Suzuki-Miyaura cross-coupling of amides by N-C(O) activation as well as in the Suzuki-Miyaura cross-coupling of esters, aryl chlorides, and Buchwald-Hartwig amination. Most crucially, this study introduces broadly available anilines as stabilizing ligands for well-defined Pd(II)-NHC catalysts. The availability of various aniline scaffolds, including structural and electronic diversity, has a significant potential in fine-tuning of challenging cross-couplings by Pd-NHCs. The parent catalyst in this class, [Pd(IPr)(AN)Cl], has been commercialized in collaboration with Millipore Sigma, offering broad access for reaction screening and optimization.
我们报道了[(NHC)PdCl(苯胺)]配合物的合成、表征及反应活性。这些定义明确、对空气和湿气稳定的催化剂在通过N-C(O)活化实现的酰胺的铃木-宫浦交叉偶联反应以及酯、芳基氯的铃木-宫浦交叉偶联反应和布赫瓦尔德-哈特维希胺化反应中具有高活性。最为关键的是，本研究引入了广泛可得的苯胺作为定义明确的Pd(II)-NHC催化剂的稳定配体。各种苯胺骨架的可得性，包括结构和电子多样性，在通过Pd-NHCs对具有挑战性的交叉偶联反应进行微调方面具有巨大潜力。此类中的母体催化剂[Pd(IPr)(AN)Cl]已与默克密理博合作实现商业化，为反应筛选和优化提供了广泛途径。
