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Configuration and E / Z interconversion mechanism of O ( S )‐allyl‐ S ( O )‐methyl‐ N ‐(acridin‐9‐yl) iminothiocarbonate
Author(s) -
Klika Karel D.,
Imrich Ján,
Danihel Ivan,
Böhm Stanislav,
Kristian Pavol,
Hamul'aková Slávka,
Pihlaja Kalevi,
Koch Andreas,
Kleinpeter Erich
Publication year - 2005
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1564
Subject(s) - chemistry , isomerization , quantum chemical , stereochemistry , inversion (geology) , computational chemistry , chemical shift , walden inversion , transition state , molecule , organic chemistry , structural basin , biology , catalysis , paleontology
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. Copyright © 2005 John Wiley & Sons, Ltd.