Copper(II) Anilides in sp3 C-H Amination

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• 作者：Eun Sil Jang ; Claire L. McMullin ; Martina K盲脽 ; Karsten Meyer ; Thomas R. Cundari ; Timothy H. Warren
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：136
• 期：31
• 页码：10930-10940
• 全文大小：666K
• ISSN：1520-5126

文摘

We report a series of novel 尾-diketiminato copper(II) anilides [Cl₂NN]Cu-NHAr that participate in C-H amination. Reaction of H₂NAr (Ar = 2,4,6-Cl₃C₆H₂ (Ar^Cl3), 3,5-(CF₃)₂C₆H₃ (Ar^F6), or 2-py) with the copper(II) t-butoxide complex [Cl₂NN]Cu-^tOBu yields the corresponding copper(II) anilides [Cl₂NN]Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: 魏¹-N in the trigonal [Cl₂NN]Cu-NHAr^Cl3 to dinuclear bridging in {[Cl₂NN]Cu}₂(渭-NHAr^F6)₂ and 魏²-N,N in the square planar [Cl₂NN]Cu(魏²-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a 蟺-stacking arrangement of [Cl₂NN]Cu-NHAr^Cl3; solution EPR data are consistent with monomeric species. Reaction of [Cl₂NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when ^tBuOO^tBu is used, which allows for HAA of R-H to occur from the ^tBuO^{鈥?/sup> radical generated by reaction of [Cl₂NN]Cu and tBuOOtBu. The principal role of these copper(II) anilides [Cl₂NN]Cu-NHAr is to capture the radical R鈥?/sup> generated from HAA by tBuO鈥?/sup> to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch鈥揝osnovsky reaction.}