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Mimics of Pincer Ligands: An Accessible Phosphine-Free <i>N</i>-(Pyrimidin-2-yl)-1,2-azole-3-carboxamide Framework for Binuclear Pd(II) Complexes and High-Turnover Catalysis in Water

Alexey V. Kletskov, Н. А. Бумагин, С. К. Петкевич, Е. А. Дикусар, Alexander S. Lyakhov, Ludmila S. Ivashkevich, И. А. Колесник, В. И. Поткин

2020Inorganic Chemistry26 citationsDOIOpen Access PDF

Abstract

We report for the first time cyclic phosphine-free “head to tail” N,N,N pincer-like (pincer complexes mimicking) N-(pyrimidin-2-yl)-1,2-azole-3-carboxamide Pd(II) complexes with deprotonated amide groups as high-turnover catalysts (TON up to 106, TOF up to 1.2 × 107 h–1) for cross-coupling reactions on the background of up to quantitative yields under Green Chemistry conditions. The potency of the described catalyst family representatives was demonstrated in Suzuki–Miyaura, Mizoroki–Heck, and Sonogashira reactions on industrially practical examples. Corresponding ligands could be synthesized based on readily available reagents through simple chemical transformations. Within the complex structures, a highly unusual 1,3,5,7-tetraza-2,6-dipalladocane frame could be observed.

Topics & Concepts

ChemistryPincer movementPhosphineCatalysisAmideCarboxamideDeprotonationAzoleCombinatorial chemistryLigand (biochemistry)Medicinal chemistryTurnover numberStereochemistryOrganic chemistryMedicineDermatologyIonBiochemistryReceptorAntifungalCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and CatalysisChemical Synthesis and Analysis
Mimics of Pincer Ligands: An Accessible Phosphine-Free <i>N</i>-(Pyrimidin-2-yl)-1,2-azole-3-carboxamide Framework for Binuclear Pd(II) Complexes and High-Turnover Catalysis in Water | Litcius