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[Fe(F 20 TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F 20 TPP)(NAr)](PhINAr)} + . Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations
Author(s) -
Liu Yungen,
Chen GuoQiang,
Tse ChunWai,
Guan Xianguo,
Xu ZhengJiang,
Huang JieSheng,
Che ChiMing
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201402580
Subject(s) - amination , chemistry , catalysis , nitrene , medicinal chemistry , rutaecarpine , organic chemistry , chromatography
Amination of CH bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for CN 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(F 20 TPP)Cl] (H 2 F 20 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 CH 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(F 20 TPP)(NC 6 H 4 ‐ p ‐NO 2 )](PhI=NC 6 H 4 ‐ p ‐NO 2 )} + .intermediate in the catalysis.