Structure - chiroptical properties relationship of cisoid enones with an alpha-methylenecyclopentanone unit
PBN-AR
Instytucja
Instytut Chemii Organicznej Polskiej Akademii Nauk
Informacje podstawowe
Główny język publikacji
en
Czasopismo
RSC Advances
ISSN
2046-2069
EISSN
Wydawca
DOI
URL
Rok publikacji
2014
Numer zeszytu
Strony od-do
43977-43993
Numer tomu
4
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Streszczenia
Język
angielski
Treść
In the present work{,} the validity of sector and helicity rules correlating the stereostructure of cis-enones containing the 2-methylenecyclopentanone unit with the sign of the n[small pi]* Cotton effect (CE) observed in their electronic circular dichroism (ECD) spectra is assessed. To this end{,} a series of model steroid cis-enones with five-membered ketone rings was synthesized. To investigate the scope and limitations of existing rules a combination of ECD spectroscopy{,} X-ray analysis{,} and time-dependent density functional theory (TD-DFT) calculations were utilized. A comparison of the experimental ECD spectra with spectra simulated by the TD-DFT calculations gave a reasonable interpretation of the n[small pi]* CE{'}s observed in the 360-335 nm spectral range. The results suggest that the previously articulated rules are not applicable to the investigated compounds. On the basis of comprehensive analysis of collected data{,} a new rule correlating perfectly the structure of studied enones with the signs of their n[small pi]* CE was proposed. This rule correlates directly the sign of the torsion angle {"}b{"} of the cyclopentanone ring of cis-enone with the sign of the n[small pi]* CE.
Cechy publikacji
ORIGINAL_ARTICLE
Inne
System-identifier
585952
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