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Hyperolactone C: Determination of its absolute configuration by comparison of experimental and calculated CD spectra
Author(s) -
Schühly Wolfgang,
Crockett Sara L.,
Fabian Walter M.F.
Publication year - 2005
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.20164
Subject(s) - chemistry , absolute configuration , polarizable continuum model , density functional theory , chirality (physics) , circular dichroism , time dependent density functional theory , polarizability , solvation , spectral line , excitation , diastereomer , enantiomer , computational chemistry , vibrational circular dichroism , molecular physics , stereochemistry , molecule , symmetry breaking , organic chemistry , quantum mechanics , physics , nambu–jona lasinio model , chiral symmetry breaking
A detailed conformational analysis of hyperolactone C diastereomers and enantiomers ((5 R ,9 R ),(5 S ,9 S ) and (5 S ,9 R ),(5 R ,9 S )) was done with molecular mechanics and density functional theory methods. Time‐dependent density functional theory (B3PW91/TZVP) was used to calculate electronic transition energies (UV/vis spectra) and rotational strengths of the respective conformations. The effect of solvation (acetonitrile solution) on excitation energies and electronic circular dichroism was approximated by the polarizable continuum model. By comparison of the simulated CD spectrum with that measured for hyperolactone C isolated from Hypericum lloydii , its absolute configuration can be assigned as (5 S ,9 S ). Chirality 17:250–256, 2005. © 2005 Wiley‐Liss, Inc.