1151967-80-4Relevant academic research and scientific papers
Iron-catalyzed intramolecular allylic C-H amination
Paradine, Shauna M.,White, M. Christina
supporting information; experimental part, p. 2036 - 2039 (2012/03/11)
A highly selective C-H amination reaction under iron catalysis has been developed. This novel system, which employs an inexpensive, nontoxic [Fe IIIPc] catalyst (typically used as an industrial ink additive), displays a strong preference for allylic C-H amination over aziridination and all other C-H bond types (i.e., allylic > benzylic > ethereal > 3° > 2° ? 1°). Moreover, in polyolefinic substrates, the site selectivity can be controlled by the electronic and steric character of the allylic C-H bond. Although this reaction is shown to proceed via a stepwise mechanism, the stereoretentive nature of C-H amination for 3° aliphatic C-H bonds suggests a very rapid radical rebound step.
A diruthenium catalyst for selective, intramolecular allylic C-H amination: Reaction development and mechanistic insight gained through experiment and theory
Harvey, Mark Edwin,Musaev, Djamaladdin G.,Du Bois
supporting information; experimental part, p. 17207 - 17216 (2011/12/13)
The mixed-valent paddlewheel complex tetrakis(2-oxypyridinato) diruthenium(II,III) chloride, [Ru2(hp)4Cl], catalyzes intramolecular allylic C-H amination with bis(homoallylic) sulfamate esters. These results stand in marked contrast to reactions performed with dirhodium catalysts, which favor aziridine products. The following discussion constitutes the first report of C-H amination using complexes such as [Ru 2(hp)4Cl] and related diruthenium adducts. Computational and experimental studies implicate a mechanism for [Ru2(hp) 4Cl]-promoted C-H amination involving hydrogen-atom abstraction/radical recombination and the intermediacy of a discrete, albeit short-lived, diradical species. The collective data offer a coherent model for understanding the preference of this catalyst to oxidize allylic (and benzylic) C-H bonds.
