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J Am Chem Soc. 2013 May 15;135(19):7194-204. doi: 10.1021/ja3122526. Epub 2013 May 2.

Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations.

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  • 1Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.

Abstract

The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4)2 (1, qpy = 2,2':6',2″:6″,2''':6''',2''''-quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp(3))-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp(3))-H bonds of hydrocarbons but also the C(sp(3))-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI═NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)](n+) (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2](2+) (CNTs) and [Fe(qpy)(NTs)](2+) (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI═NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate CNTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.

PMID:
23634746
[PubMed]
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