Chiroptical Study and Absolute Configuration of (−)–O‐DMA Produced From Daidzein Metabolism. Issue 9 (12th February 2014)

• Record Type: Journal Article
• Authors: Kim, Mihyang; Han, Jaehong
• Is Part Of: Chirality. Volume 26:Issue 9(2014:Sep.)
• Page Start: 74
• Page End: 77
• Publication Date: 2014-02-12
• Subjects: Chirality -- Periodicals; Pharmaceutical chemistry -- Periodicals; 541.22
• DOI: 10.1002/chir.22295
• Languages: English
• ISSNs: 0899-0042

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>To elucidate the hitherto unknown absolute configuration of (−)–<italic>O</italic>‐desmethylangolensin ((−)–<italic>O</italic>‐DMA), an intestinal bacterial metabolite produced from daidzein, chiroptical study, including specific optical rotation and electronic circular dichroism (ECD), of (<italic>R</italic>)–<italic>O</italic>‐DMA was carried out by Time‐Dependent Density Functional Theory (TD‐DFT) calculations. <named-content content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">Intramolecular</named-content> hydrogen bonding between 2'–OH and carbonyl oxygen at 1‐C of <italic>O</italic>‐DMA was a governing factor for <italic>O</italic>‐DMA to form the stable conformations. Total energy values of four possible conformers were calculated in the framework of DFT using the B3LYP exchange correlation functional at the 6‐31++G basis set level. The theoretical specific rotation and ECD spectra of all conformers in ethanol were obtained by TD‐DFT calculation using B3LYP functional at the 6‐311++G basis set level, and compared to the experimental data. Chiroptical properties of (<italic>R</italic>)–<italic>O</italic>‐DMA showed a good agreement with the biological (−)–<italic>O</italic>‐DMA. Therefore, the stereospecific biosynthetic pathway of (−)–<italic>O</italic>‐DMA was proposed as daidzein → (<italic>R</italic>)‐dihydrodaidzein ↔ (<italic>S</italic>)‐dihydrodaizein → (<italic>R</italic>)–<italic>O</italic>‐DMA. <italic>Chirality 26:74–77, 2014</italic>. © 2014 Wiley Periodicals, Inc.</p> </abstract>