title: Highly selective intramolecular carbene insertion into primary C-H bond of α-diazoacetamides mediated by a (p-cymene)ruthenium(II) carboxylate complex.
abstract: Complex [(p-cymene)Ru(η(1)-O(2)CCF(3))(2)(OH(2))] mediated transformation of α-diazoacetamides ArCH(2)N(C(CH(3))(3))C(O)CHN(2) to result in carbene insertion into the primary C-H bond exclusively, with the γ-lactam products being isolated in up to 98% yield. This unexpected reaction is striking in view of the presence of usually more reactive sites such as secondary C-H bonds in the substrates. DFT calculations based on proposed Ru-carbene species provide insight into this unique selectivity.
authors.affiliation: Department of Chemistry, State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
authors.forename: Vanessa Kar-Yan
authors.initials: VK
authors.lastname: Lo
authors.forename: Zhen
authors.initials: Z
authors.lastname: Guo
authors.forename: Matthew Kwok-Wai
authors.initials: MK
authors.lastname: Choi
authors.forename: Wing-Yiu
authors.initials: WY
authors.lastname: Yu
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
mesh_terms: D000081:Acetamides / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry; D000081007:Cymenes; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D039821:Monoterpenes / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D000081:Acetamides; D001391:Azo Compounds; D002264:Carboxylic Acids; D056831:Coordination Complexes; D000081007:Cymenes; D039821:Monoterpenes; C007210:4-cymene; C030011:carbene; D012428:Ruthenium; D008697:Methane