title: Kinetic and mechanistic studies of NEt3-catalyzed intramolecular aminolysis of carbamate.
abstract: The mechanism of the NEt 3-catalyzed intramolecular aminolysis of Z- 1 in acetonitrile or aqueous acetonitrile solutions is suggested to involve rate-determining collapse of T (+/-) through simultaneous H-abstraction and ethoxide expulsion of E2 process. The evidence for that includes the primary isotope effect of k H/ k D = 1.66 in acetonitrile, general-base catalysis in aqueous buffer solutions, salt effect, and the proposed water-stabilized rate-determining transition states (TS1 and TS2) in the water-titration experiments.
authors.affiliation: Department of Chemistry, National Cheng Kung University, Tainan, Taiwan. kssung@mail.ncku.edu.tw
authors.forename: Kuangsen
authors.initials: K
authors.lastname: Sung
authors.forename: Bo-Ren
authors.initials: BR
authors.lastname: Zhuang
authors.forename: Pin-Mei
authors.initials: PM
authors.lastname: Huang
authors.forename: Sheng-Wei
authors.initials: SW
authors.lastname: Jhong
mesh_terms: D000588:Amines / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000588:Amines; D002219:Carbamates