A Structure鈥揂ctivity Study of Ni-Catalyzed Alkyl鈥揂lkyl Kumada Coupling. Improved Catalysts for Coupling of Secondary Alkyl Halides

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• 作者：Peng Ren ; Oleg Vechorkin ; Kim von Allmen ; Rosario Scopelliti ; Xile Hu
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：May 11, 2011
• 年：2011
• 卷：133
• 期：18
• 页码：7084-7095
• 全文大小：1223K
• 年卷期：v.133,no.18(May 11, 2011)
• ISSN：1520-5126

文摘

A structure鈥揳ctivity study was carried out for Ni catalyzed alkyl鈥揳lkyl Kumada-type cross coupling reactions. A series of new nickel(II) complexes including those with tridentate pincer bis(amino)amide ligands (^RN₂N) and those with bidentate mixed amino-amide ligands (^RNN) were synthesized and structurally characterized. The coordination geometries of these complexes range from square planar, tetrahedral, to square pyramidal. The complexes had been examined as precatalysts for cross coupling of nonactivated alkyl halides, particularly secondary alkyl iodides, with alkyl Grignard reagents. Comparison was made to the results obtained with the previously reported Ni pincer complex [(^MeN₂N)NiCl]. A transmetalation site in the precatalysts is necessary for the catalysis. The coordination geometries and spin-states of the precatalysts have a small or no influence. The work led to the discovery of several well-defined Ni catalysts that are significantly more active and efficient than the pincer complex [(^MeN₂N)NiCl] for the coupling of secondary alkyl halides. The best two catalysts are [(^HNN)Ni(PPh₃)Cl] and [(^HNN)Ni(2,4-lutidine)Cl]. The improved activity and efficiency was attributed to the fact that phosphine and lutidine ligands in these complexes can dissociate from the Ni center during catalysis. The activation of alkyl halides was shown to proceed via a radical mechanism.