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Ab initio calculations for the optical rotations of conformationally flexible molecules: A case study on six‐, seven‐, and eight‐membered fluorinated cycloalkanol esters
Author(s) -
Grimme Stefan,
Bahlmann Arnold,
Haufe Günter
Publication year - 2002
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.10140
Subject(s) - chemistry , optical rotation , molecule , ab initio , ring (chemistry) , enantiomer , computational chemistry , absolute configuration , rotation (mathematics) , absolute deviation , density functional theory , ab initio quantum chemistry methods , molecular physics , crystallography , stereochemistry , organic chemistry , geometry , mathematics , statistics
Based on the time‐dependent density functional response theory, an approach for the prediction of optical rotations of enantiomers of conformationally flexible molecules was developed. The method was applied successfully for the determination of the absolute configuration of trans ‐2‐fluorocycloalkanol acetates with different ring rizes. The largest deviations between experimental and theoretical [α] D values are 10 deg. · [dm · (g/cc)] −1 (about 20% error). These theoretical results suggest that the optical rotation in these molecules is dominated by the local (1 R; 2 R ) configuration of the two substituents and that different ring and even axial/equatorial orientations play a less important role. Chirality 14:793–797, 2002. © 2002 Wiley‐Liss, Inc.