Determination of absolute configuration of conformationally flexible cis-dihydrodiol metabolites: effect of diene substitution pattern on the circular dichroism spectra and optical rotations.
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, 1H 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.
Kwit
Marcin
M
Department of Chemistry, A. Mickiewicz University, Poznan, Poland.
Sharma
Narain D
ND
Boyd
Derek R
DR
Gawronski
Jacek
J
D001555:Benzene Derivatives / Q000737:chemistry; D002942:Circular Dichroism; D053138:Cyclohexenes / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D009904:Optical Rotation; D013237:Stereoisomerism; D013816:Thermodynamics
D001555:Benzene Derivatives; D053138:Cyclohexenes; D009281:Naphthalenes; C507866:trans-1,2-dihydro-1,2-naphthalenediol