[Fe(F20TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F20TPP)(NAr)](PhINAr)} + . Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations. Issue 1 (11th September 2014)

• Record Type: Journal Article
• Authors: Liu, Yungen; Chen, Guo‐Qiang; Tse, Chun‐Wai; Guan, Xianguo; Xu, Zheng‐Jiang; Huang, Jie‐Sheng; Che, Chi‐Ming
• Is Part Of: Chemistry, an Asian journal. Volume 10:Issue 1(2015:Jan.)
• Page Start: 100
• Page End: 105
• Publication Date: 2014-09-11
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201402580
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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)<sub>2</sub>+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)<sub>2</sub>+primary arylamines' amination protocol has been developed using [Fe(F<sub>20</sub>TPP)Cl] (H<sub>2</sub>F<sub>20</sub>TPP=<italic>meso</italic>‐tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra‐ and intermolecular amination of sp<sup>2</sup> and sp<sup>3</sup> 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(F<sub>20</sub>TPP)(NC<sub>6</sub>H<sub>4</sub>‐<italic>p</italic>‐NO<sub>2</sub>)](PhI=NC<sub>6</sub>H<sub>4</sub>‐<italic>p</italic>‐NO<sub>2</sub>)}<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh2xpp2v31" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:18614728:media:ASIA201402580:tex2gif-sup-5" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>+</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>.</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msup></mml:math></alternatives></inline-formula> intermediate in the catalysis.</p> </abstract>