1215209-38-3Relevant articles and documents
Copper(II) anilides in sp3 C-H amination
Jang, Eun Sil,McMullin, Claire L.,K??, Martina,Meyer, Karsten,Cundari, Thomas R.,Warren, Timothy H.
, p. 10930 - 10940 (2014/08/18)
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 (ArF6), 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-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}2(μ-NHArF6)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- NHArCl3; 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 tBuOOtBu is used, which allows for HAA of R-H to occur from the tBuO? radical generated by reaction of [Cl 2NN]Cu and tBuOOtBu. 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.
Catalytic C - H amination with unactivated amines through copper(II) amides
Wiese, Stefan,Badiei, Yosra M.,Gephart, Raymond T.,Mossin, Susanne,Varonka, Matthew S.,Melzer, Marie M.,Meyer, Karsten,Cundari, Thomas R.,Warren, Timothy H.
, p. 8850 - 8855 (2011/02/24)
En route to catalysis: Two equivalents of the three-coordinate copper(II) amide [(Cl2NN)Cu]-NHAd participate in stoichiometric C - H amination by a H-atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert-butoxide intermediate to allow for the unprecedented catalytic amination of sp3-C - H bonds with unactivated alkylamines. This method greatly expands the range of amines for catalytic C - H amination since most protocols require N-based electron-withdrawing groups.
