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Theoretical studies of iron(iii)-catalyzed intramolecular C-H amination of azides

Dalton Transactions, ISSN: 1477-9226, Vol: 42, Issue: 40, Page: 14369-14373
2013
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Density functional theory calculations have been carried out to study the reaction mechanism of the [Fe(FTPP)Cl] catalyzed C-H amination reaction. The calculations show that the classical three-step mechanism for other metals (Ru, Rh, Ir and Zn), including N liberation, C-N bond formation and 1,2-hydrogen shift, does not fit the iron(iii)-catalyzed system. After N liberation, the favorable reaction pathway for the iron(iii)-catalyzed system is a 1,2-hydrogen shift preceding C-N bond formation, i.e., a H-abstraction/radical rebound mechanism. © 2013 The Royal Society of Chemistry.

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