The nature of persistent conformational chirality, racemization mechanisms, and predictions in diarylether heptanoid cyclophane natural products

The nature of persistent conformational chirality, racemization mechanisms, and predictions in diarylether heptanoid cyclophane natural products

Restricted rotations of chemical bonds can lead to the presence of persistent conformational chirality in molecules lacking stereocenters. We report the development of first-of-a-kind predictive rules that enable identification of conformational chirality and prediction of racemization barriers in t...

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Bibliographic Details
Published in:Organic & biomolecular chemistry Vol. 12; no. 20; p. 3303
Main Authors: Pattawong, Ommidala, Salih, M Quamar, Rosson, Nicholas T, Beaudry, Christopher M, Cheong, Paul Ha-Yeon
Format: Journal Article
Language:English
Published: England 28-05-2014
Subjects:
Biological Products - chemistry
Diarylheptanoids - chemistry
Ethers, Cyclic - chemistry
Hydrogen Bonding
Kinetics
Molecular Conformation
Stereoisomerism
Thermodynamics
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Summary:Restricted rotations of chemical bonds can lead to the presence of persistent conformational chirality in molecules lacking stereocenters. We report the development of first-of-a-kind predictive rules that enable identification of conformational chirality and prediction of racemization barriers in the diarylether heptanoid (DAEH) natural products that do not possess stereocenters. These empirical rules-of-thumb are based on quantum mechanical computations (SCS-MP2/∞//B3LYP/6-31G*/PCM) of racemization barriers of four representative DAEHs. Specifically, the local symmetry of ring B and the E/Z configuration of the vinylogous acid/ester are critical in determining conformational chirality in the DAEH natural product family.
ISSN:1477-0539
DOI:10.1039/c3ob42550a