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The Nature of Persistent Conformational Chirality, Racemization Mechanisms, and Predictions in Diarylether Heptanoid Cyclophane Natural Products

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  • Restricted rotations of chemical bonds can lead to the presence of persistent conformational chirality in molecules 10 lacking stereocenters. We report the development of first-ofa- 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 15 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 20 determining conformational chirality in the DAEH natural product family. Molecular chirality is of paramount importance to chemistry, biology, and medicine. Small molecules that are chiral by virtue of restricted rotations (atropisomerism), or conformational 25 chirality, are an underdeveloped territory with the potential for new developments of chiral ligands, medicinal compounds, catalysts, and materials. At present, there are no known methods to predict the presence of persistent conformational chirality in these compounds based solely on their molecular architecture 30 without resorting to total synthesis. Specifically in this report, we have developed predictive rules-of-thumb for the chiral properties of all members in a family of cyclophane natural products called the diarylether heptanoids (DAEHs). Additionally, we elucidate the atomistic and energetic details 35 related to the racemizations.
  • This is an author's peer-reviewed final manuscript, as accepted by the publisher.
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  • Pattawong, O., Salih, M. Q., Rosson, N. T., Beaudry, C. M., & Cheong, P. H. Y. (2014). The nature of persistent conformational chirality, racemization mechanisms, and predictions in diarylether heptanoid cyclophane natural products. Organic & Biomolecular Chemistry, 12(20), 3303-3309. doi:10.1039/c3ob42550a
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  • 12
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  • 20
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  • The published article can be found at Organic & Biomolecular Chemistry.
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