title: Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl) iminothiocarbonate.
abstract: The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S-allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the r(NOE). Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case-by-case basis.
authors.affiliation: Department of Chemistry, University of Turku, FIN-20014 Turku, Finland.
authors.forename: Karel D
authors.initials: KD
authors.lastname: Klika
authors.forename: Ján
authors.initials: J
authors.lastname: Imrich
authors.forename: Ivan
authors.initials: I
authors.lastname: Danihel
authors.forename: Stanislav
authors.initials: S
authors.lastname: Böhm
authors.forename: Pavol
authors.initials: P
authors.lastname: Kristian
authors.forename: Slávka
authors.initials: S
authors.lastname: Hamul'aková
authors.forename: Kalevi
authors.initials: K
authors.lastname: Pihlaja
authors.forename: Andreas
authors.initials: A
authors.lastname: Koch
authors.forename: Erich
authors.initials: E
authors.lastname: Kleinpeter