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Resolution, Enantiomerization Kinetics, and Chiroptical Properties of 7,7‘-Dihydroxy-8,8‘-biquinolyl
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Section:Abstract
(±)-7,7‘-Dihydroxy-8,8‘-biquinolyl (6) was resolved into its enantiomorphic atropisomers via reverse phase (C18) chromatographic separation of epimeric bismenthyl carbonates, (−)-lk-9 and (+)-ul-9, derived from 6 and (+)-menthyl chloroformate. The faster eluting diastereoisomer, (−)-lk-9, was revealed to possess an (aS)-configurated biaryl axis by X-ray crystallographic analysis. Saponification of the separated bismenthyl carbonates gave enantioenriched samples of biquinolyl 6, and absolute stereochemical configurations were assigned to the two optical isomers as (−)-(aS)-6 and (+)-(aR)-6 by correlation with their respective progenitors, (−)-lk-9 and (+)-ul-9. First-order rate constants for the enantiomerization of 6 in water were obtained over the temperature range 316−366 K, and activation parameters were determined as ΔH = 34.0 kcal mol-1 and ΔS
= 18.7 cal mol-1 K-1 by Eyring plot analysis. A low level (AM1) computational study of the rotational dynamics of 6 showed excellent agreement with kinetic experimental data and suggested that enantiomerization occurs preferentially via a syn pathway. In common with (−)-(aS)-1,1‘-bi-2-naphthol (BINOL), (−)-(aS)-6 showed positive exciton chirality in its electronic circular dichroism (CD) spectrum and gave a characteristic couplet composed of a positive maximum Cotton effect at 250 nm and a negative minimum at 234 nm (ΔΔε = +40 M-1 cm-1 at 64% ee).
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This article has been cited by 5 ACS Journal articles (5 most recent appear below).
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Design, Synthesis and Optical Resolution of New Bifunctional Ligand: 1,1′-Dimethyl-octahydro-8,8′-Biquinoline-7,7′-diol
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Jian Xiao and Teck-Peng LohOrganic Letters2009 11 (13), 2876-2879The design, synthesis and optical resolution of a new bifunctional ligand, 1,1′-dimethyl-octahydro-8,8′-biquinoline-7,7′-diol, is described. This new aza analogue of BINOL exhibits different properties as compared to BINOL.
Chemoselective Functionalization of 3,3′-Substituted BINOL Derivatives
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Carmine Coluccini, Antonio Castelluccio and Dario PasiniThe Journal of Organic Chemistry2008 73 (11), 4237-4240An efficient chemoselective differentiation of vicinal phenolic and benzylic alcohols on optically active binaphthyl skeletons has been achieved via TBS protection of the less sterically hindered, external 3,3′ benzylic positions. Further manipulation ...
Enzymatic Resolution of 7,7‘-Dihydroxy-8,8‘- biquinolyl Dipentanoate and Its Conversion to 2,2‘-Di-tert-butyl-7,7‘-dihydroxy-8,8‘-biquinolyl
Paul R. Blakemore, Selena D. Milicevic, and Lev N. ZakharovThe Journal of Organic Chemistry2007 72 (24), 9368-9371Enzymatic Resolution of 7,7‘-Dihydroxy-8,8‘- biquinolyl Dipentanoate and Its Conversion to 2,2‘-Di-tert-butyl-7,7‘-dihydroxy-8,8‘-biquinolyl
Paul R. Blakemore, Selena D. Milicevic, and Lev N. ZakharovThe Journal of Organic Chemistry2007 72 (24), 9368-9371Incubation of ()-7,7-di(pentanoyloxy)-8,8-biquinolyl (4) with a crude cholesterol esterase preparation (from bovine pancreas) yielded highly enantioenriched unreacted dextrorotatory material, (+)-(aR)-4 (46%, 99% ee), accompanied by the expected diol ...
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- Published In Issue October 13, 2006
- Received August 2, 2006
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