Kletskov Alexey V, Bumagin Nikolay A, Petkevich Sergey K, Dikusar Evgenij A, Lyakhov Alexander S, Ivashkevich Ludmila S, Kolesnik Iryna A, Potkin Vladimir I
Chemical Department, M.V. Lomonosov Moscow State University, Leninskie Gory, 1/3, Moscow 119991, Russian Federation.
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Surganova Str., 13, Minsk 220072, Belarus.
Inorg Chem. 2020 Aug 3;59(15):10384-10388. doi: 10.1021/acs.inorgchem.0c01035. Epub 2020 Jul 20.
We report for the first time cyclic phosphine-free "head to tail" N,N,N pincer-like (pincer complexes mimicking) -(pyrimidin-2-yl)-1,2-azole-3-carboxamide Pd(II) complexes with deprotonated amide groups as high-turnover catalysts (TON up to 10, TOF up to 1.2 × 10 h) 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.
我们首次报道了不含环膦的“头对尾”N,N,N钳状（模拟钳形配合物）-(嘧啶-2-基)-1,2-唑-3-甲酰胺钯(II)配合物，其具有去质子化酰胺基团，作为高周转催化剂（TON高达10，TOF高达1.2×10 h）用于交叉偶联反应，在绿色化学条件下产率高达定量。在铃木-宫浦、水泽-赫克和索尼加什ira反应的工业实际例子中证明了所述催化剂家族代表的效力。相应的配体可以通过简单的化学转化，基于容易获得的试剂合成。在复杂结构中，可以观察到一个非常不寻常的1,3,5,7-四氮杂-2,6-二钯环烷骨架。
