Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl) iminothiocarbonate

✍ Scribed by Karel D. Klika; Ján Imrich; Ivan Danihel; Stanislav Böhm; Pavol Kristian; Slávka Hamul'aková; Kalevi Pihlaja; Andreas Koch; Erich Kleinpeter

• Book ID: 102531395
• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 341 KB
• Volume: 43
• Category: Article
• ISSN: 0749-1581
• DOI: 10.1002/mrc.1564

✦ Synopsis

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.