Chiral Gas Chromatographic Separation of 2-Oxabicyclo[3.3.0]octane Derivatives and Their Synthetic Precursors
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- 作者：Maria Conceiç ; ã ; o K. V. Ramos ; Edson F. Silva ; Francisco R. Aquino Neto ; Emerson P. Peç ; anha ; Carlos R. Rodrigues ; Eliezer J. Barreiro ; and Carlos A. M. Fraga
- 刊名：Analytical Chemistry
- 出版年：2000
- 出版时间：July 15, 2000
- 年：2000
- 卷：72
- 期：14
- 页码：3056 - 3062
- 全文大小：253K
- 年卷期：v.72,no.14(July 15, 2000)
- ISSN：1520-6882
文摘
Chiral GC separation of (±)-2-allyl-2-carboethoxycyclopentanone (9) and the alcohols (±)-3-(hydroxymethyl)-5-carboethoxy-2-oxabicyclo[3.3.0]octane (7), (±)-2-allyl-2-carboethoxycyclopentanol (8), and their acetylated andtrifluoroacetylated derivatives were investigated on threederivatized 
mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-cyclodextrins (CDs) diluted in SE-54 or1701-OH: 2,3,6-tri-O-methyl-mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-CD (PMCD); 2,3-di-O-methyl-6-O-(tert-butyldimethylsilyl)-mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-CD (DIMETBCD);2,3-di-O-acetyl-6-O-(tert-butyldimethylsilyl)-mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-CD (DIACTBCD). The understanding of these chiral separationsis extremelly relevant, since cyclopentanic and bicycliccyclopentanic rings are common structural features ofmany important natural products and new pharmaceuticaldrugs. In general DIMETBCD diluted in SE-54 showedthe best chiral resolution to alcohols 7 and 8 and onlyDIACTBCD showed enantioselectivity to 9. Hydrogenbonds prediction and dipole moments data were obtainedby molecular modeling calculations for 7ab and 8ab andAc and TFA derivatives. Comparison of these data withthe chromatographic parameters for the related compounds were used to explain the differences of theirelution orders and diastereo- and enantiomeric separations on the above chiral stationary phases (CSPs). Theresults suggest that the CSPs enantioselectivities are notaffected by the carboethoxy-functionalized cyclopentanicand bicyclic cyclopentanic rings themselves but mainlyby the functional group on the other stereogenic center.