Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex-Catalyzed Hydroarsination Reaction.,Chemistry - A European Journal

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Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex-Catalyzed Hydroarsination Reaction.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2019-08-01 , DOI: 10.1002/chem.201902138
Wee Shan Tay ₁ , Yunpeng Lu ₁ , Xiang-Yuan Yang ₁ , Yongxin Li ₁ , Sumod A Pullarkat ₁ , Pak-Hing Leung ₁

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Synthetic challenges have significantly slowed the development of the catalytic asymmetric hydroarsination reaction despite it being a highly attractive C-As bond formation methodology. In addition, there is a poor understanding of the main reaction steps in such reactions which limit further development in the field. Herein, key intermediates of the hydroarsination reaction catalyzed by a PCP NiII -Cl pincer complex are presented upon investigating the reaction with DFT calculations, conductivity measurements, NMR spectroscopy, and catalytic screening. The novel Ni-Cl-As interaction proposed was then contrasted against known NiII -catalyzed hydrophosphination reactions to highlight dissimilarities between them even though P and As share a close group relationship. Lastly, the asymmetric hydroarsination of nitroolefins was further developed to furnish a library of chiral organoarsines in up to 99 % yield and 80 % ee under mild conditions (-20 °C to RT) between 5 to 210 mins.

中文翻译：

镍（II）钳配合物催化的氢化砷化反应的催化和机理研究。

尽管合成挑战是一种极具吸引力的C-As键形成方法，但它极大地减缓了催化不对称加氢砷化反应的发展。另外，对于此类反应中的主要反应步骤知之甚少，这限制了该领域的进一步发展。在此，在通过DFT计算，电导率测量，NMR光谱和催化筛选研究反应时，给出了由PCP NiII -Cl夹杂物催化的氢化砷化反应的关键中间体。然后将提出的新颖的Ni-Cl-As相互作用与已知的NiII催化的氢磷酸化反应进行对比，以突出它们之间的差异，即使P和As具有密切的基团关系。最后，

更新日期：2019-08-01

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