title: Controlling diaza-Cope rearrangement reactions with resonance-assisted hydrogen bonds.
abstract: NMR studies reveal that the equilibrium between 1 and 2 lies essentially toward 1 to the left without any detectable amount of 2. DFT computation shows that the value of K1 is about 1.4 x 10-5, and X-ray crystal structures show that the resonance-assisted hydrogen bond (RAHB) in 1 (1.66 A) is shorter than the regular hydrogen bond in 2 (1.75 A). The enormous selectivity can be explained in terms of the strength of the RAHBs in 1 compared to that of the regular hydrogen bonds in 2.
authors.affiliation: Department of Chemistry, 80 St. George Street, Toronto M5S 3H6, Canada. jchin@chem.utoronto.ca
authors.forename: Jik
authors.initials: J
authors.lastname: Chin
authors.forename: Fabrizio
authors.initials: F
authors.lastname: Mancin
authors.forename: Nirusha
authors.initials: N
authors.lastname: Thavarajah
authors.forename: Donghyung
authors.initials: D
authors.lastname: Lee
authors.forename: Alan
authors.initials: A
authors.lastname: Lough
authors.forename: Doo Soo
authors.initials: DS
authors.lastname: Chung