Copper(II) anilides in sp3 C-H amination

Eun Sil Jang, Claire L. McMullin, Martina Käß, Karsten Meyer, Thomas R. Cundari, Timothy H. Warren

Research output: Contribution to journalArticlepeer-review

67 Citations (Scopus)

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 (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.

Original languageEnglish
Pages (from-to)10930-10940
Number of pages11
JournalJournal of the American Chemical Society
Volume136
Issue number31
DOIs
Publication statusPublished - 6 Aug 2014

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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