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Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction
Author(s) -
Tay Wee Shan,
Lu Yunpeng,
Yang XiangYuan,
Li Yongxin,
Pullarkat Sumod A.,
Leung PakHing
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902138
Subject(s) - pincer movement , catalysis , nickel , yield (engineering) , chemistry , combinatorial chemistry , reaction mechanism , computational chemistry , organic chemistry , materials science , metallurgy
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 Ni II ‐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 Ni II ‐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.