title: [Fe(F20 TPP)Cl]-catalyzed amination with arylamines and {[Fe(F20 TPP)(NAr)](PhI=NAr)} + . Intermediate assessed by high-resolution ESI-MS and DFT calculations.
abstract: Amination of CH bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for CN bond formation, and the use of iminoiodinanes, or their in situ generated forms from 'PhI(OAc)2 +primary amides (such as sulfonamides, sulfamates, and carbamates)', as nitrogen sources for the amination reaction has been well documented. In this work, a 'metal catalyst+PhI(OAc)2 +primary arylamines' amination protocol has been developed using [Fe(F20 TPP)Cl] (H2 F20 TPP=meso-tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra- and intermolecular amination of sp(2) and sp(3) CH bonds (>27 examples), affording the amination products, including natural products such as rutaecarpine, in moderate-to-good yields. ESI-MS analysis and DFT calculations lend support for the involvement of {[Fe(F20 TPP)(NC6 H4 -p-NO2 )](PhI=NC6 H4 -p-NO2 )} + . intermediate in the catalysis.
authors.affiliation: Department of Chemistry, State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (P. R. China), Fax: (+852) 2857-1586.
authors.forename: Yungen
authors.initials: Y
authors.lastname: Liu
authors.forename: Guo-Qiang
authors.initials: GQ
authors.lastname: Chen
authors.forename: Chun-Wai
authors.initials: CW
authors.lastname: Tse
authors.forename: Xianguo
authors.initials: X
authors.lastname: Guan
authors.forename: Zheng-Jiang
authors.initials: ZJ
authors.lastname: Xu
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
keywords: CH bond; amination; arylamine; catalysis; nitrene/imide; porphyrin