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Determination of the Stereostructure of Pyrimidine Nucleoside Derivatives with a Combination of Various Chiroptical Methods
Author(s) -
Górecki Marcin,
KarczmarskaWódzka Aleksandra,
Kołodziejska Renata,
Dramiński Marcin,
Frelek Jadwiga
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201402190
Subject(s) - chemistry , conformational isomerism , absolute configuration , circular dichroism , vibrational circular dichroism , pyrimidine , spectroscopy , nucleoside , computational chemistry , stereochemistry , molecule , organic chemistry , physics , quantum mechanics
The absolute configuration of pyrimidine nucleoside derivatives prepared by enantioselective reduction was determined using a combination of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectroscopy in tandem with quantum chemical calculations. Such a combined approach based on a comparison of experimentally measured and theoretically simulated chiroptical properties allows reliable predictions of absolute configuration. The advantage of using more than one chiroptical method for the assignment of absolute configuration is demonstrated. The reliability of the proposed assignment was further confirmed by ECD measurements at variable temperatures and the use of Moscowitz procedure. This allowed the relative energies of the conformers obtained from the calculations to be verified, and the distribution of conformers to be estimated.