title: A diruthenium catalyst for selective, intramolecular allylic C-H amination: reaction development and mechanistic insight gained through experiment and theory.
abstract: The mixed-valent paddlewheel complex tetrakis(2-oxypyridinato)diruthenium(II,III) chloride, [Ru(2)(hp)(4)Cl], 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)(4)Cl] and related diruthenium adducts. Computational and experimental studies implicate a mechanism for [Ru(2)(hp)(4)Cl]-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.
authors: Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
authors: Mark Edwin
authors: ME
authors: Harvey
authors: Djamaladdin G
authors: DG
authors: Musaev
authors: J
authors: J
authors: Du Bois
mesh_terms: D000586:Amination; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000588:Amines; D009942:Organometallic Compounds; D012428:Ruthenium