Copper(II) anilides in sp3 C-H amination

Jang ES, Mcmullin CL, Käß M, Meyer K, Cundari TR, Warren TH (2014)

Publication Type: Journal article

Publication year: 2014

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 136

Pages Range: 10930-10940

Journal Issue: 31

DOI: 10.1021/ja5026547

Abstract

We report a series of novel β-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H 2NAr (Ar = 2,4,6-Cl3C6H2 (Ar ^Cl3), 3,5-(CF3)2C6H3 (Ar^F6), or 2-py) with the copper(II) t-butoxide complex [Cl 2NN]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: κ¹-N in the trigonal [Cl2NN]Cu-NHAr^Cl3 to dinuclear bridging in {[Cl2NN]Cu}2(μ-NHAr^F6)2 and κ²-N,N in the square planar [Cl2NN] Cu(κ²-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a π-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• radical generated by reaction of [Cl 2NN]Cu and ^tBuOO^tBu. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R• generated from HAA by ^tBuO• to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction. © 2014 American Chemical Society.

Authors with CRIS profile

Martina Käß Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Georgetown University

United States (USA) (US) University of North Texas (UNT)

United States (USA) (US)

How to cite

APA:

Jang, E.S., Mcmullin, C.L., Käß, M., Meyer, K., Cundari, T.R., & Warren, T.H. (2014). Copper(II) anilides in sp3 C-H amination. Journal of the American Chemical Society, 136(31), 10930-10940. https://dx.doi.org/10.1021/ja5026547

MLA:

Jang, Eun Sil, et al. "Copper(II) anilides in sp3 C-H amination." Journal of the American Chemical Society 136.31 (2014): 10930-10940.

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