Determination of absolute configuration of conformationally flexible cis-dihydrodiol metabolites: Effect of diene substitution pattern on the circular dichroism spectra and optical rotations

✍ Scribed by Marcin Kwit; Narain D. Sharma; Derek R. Boyd; Jacek Gawronski

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 332 KB
• Volume: 20
• Category: Article
• ISSN: 0899-0042
• DOI: 10.1002/chir.20471

✦ Synopsis

Abstract

Absolute configurations of a number of cis‐dihydrodiols (cis‐1,2‐dihydroxy‐3,5‐cyclohexadienes), synthetically useful products of TDO‐catalyzed dihydroxylations of 1,2‐ and 1,3‐disubstituted benzene derivatives, have been determined by a comparison of calculated and experimental CD spectra and optical rotations and by methods involving X‐ray crystallography, ^1^H NMR spectra of diastereoisomeric derivatives, and by stereochemical correlations. The computations disclosed a significant effect of the substituents on conformational equilibria of cis‐dihydrodiols and chiroptical properties of individual conformers. The assigned absolute configurations of cis‐dihydrodiols have allowed the validity of a simple predictive model for TDO‐catalyzed arene dihydroxylations to be extended. Chirality, 2008. © 2007 Wiley‐Liss, Inc.