1340518-91-3Relevant academic research and scientific papers
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
, p. 17207 - 17216 (2011)
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.
