Permethyl‐β‐cyclodextrin, Chemically Bonded to Polysiloxane: a Chiral Stationary Phase with Wider Application Range for Enantiomer Separation by Capillary Gas Chromatography

Fischer, Peter; Aichholz, Reiner; Bölz, Uwe; Juza, Markus; Krimmer, Sigfried

doi:10.1002/anie.199004271

Cited by 83 publications

(19 citation statements)

References 20 publications

(1 reference statement)

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“…IϪVI -eicosa-O-methylcyclomaltoheptaose (3) (500 mg, 0.35 mmol), which was prepared by adapting the procedure of Bradshaw and co-workers, [50,52] in anhydrous THF (20 mL) was added dropwise to a stirred mixture of sodium hydride (17 mg, 0.70 mmol, washed with THF) in anhydrous THF (10 mL Figure 6. Gas chromatographic separation of the enantiomers of neomenthol (3,4), menthol (5,6), and isomenthol (7,8) in the presence of the reference standards n-dodecane (1) and n-tridecane (11,12), and 2-ethylhexanoic (13,14) in the presence of the reference standards n-undecane (9) and ndodecane (10) and O-2-Chirasil-β-Dex (bottom) (carrier gas: dihydrogen; for additional gas chromatographic data, see Table 5) …”

Section: Methodsmentioning

confidence: 99%

“…[20] Finally, Chirasil-Dex has been employed to coat silica particles and the CSP can be used in micro-packed LC, [21] packed CEC, [22] as well as sintered [23] or sol-gel-processed monolithic CEC. [24] The first preparations of Chirasil-Dex contained trimethylene, [9,10] pentamethylene, [10] and octamethylene [10] spacers juxtaposed between the permethylated cyclodextrin and the polysiloxane backbone. Recently, an undecamethylene spacer has also been utilized.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, NMR Spectroscopic Characterization and Polysiloxane‐Based Immobilization of the Three Regioisomeric Monooctenylpermethyl‐β‐cyclodextrins and Their Application in Enantioselective GC

Cousin¹,

Trapp

Peulon-Agasse³

et al. 2003

Eur J Org Chem

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2I−VI,3I−VII,6I−VII‐Eicosa‐O‐methyl‐2I‐O‐(oct‐7‐enyl)cyclomaltoheptaose, 2I−VII,3I−VI,6I−VII‐eicosa‐O‐methyl‐3I‐O‐(oct‐7‐enyl)cyclomaltoheptaose, and 2I−VII,3I−VII,6I−VI‐eicosa‐O‐methyl‐6I‐O‐(oct‐7‐enyl)cyclomaltoheptaose were synthesized by selective introduction of an oct‐7‐enyl group at one of the O‐2, O‐3, or O‐6 positions of selectively methylated cyclomaltoheptaose (β‐cyclodextrin, CD) and, depending on the synthetic route, by a subsequent permethylation step. Each of the regioisomeric mono‐oct‐7‐enylated permethylated β‐cyclodextrin derivatives was anchored by hydrosilylation to a hydridomethyldimethylsiloxane copolymer to yield unambiguously O‐2‐, O‐3‐, and O‐6‐bonded chiral stationary phases (CSP) of Chirasil‐Dex, which were evaluated in enantioselective gas chromatography (GC). O‐6‐Chirasil‐Dex displayed slightly inferior enantioselectivity relative to either O‐3‐ or O‐2‐Chirasil‐Dex. The statistical synthesis of the CSP by mono‐oct‐7‐enylation of β‐CD under varying reactions conditions (base, solvent), without the use of hydroxy group protection chemistry, furnished a mixture of O‐6‐ and O‐2‐Chirasil‐Dex in dimethylformamide and predominantly the O‐2‐regioisomer in dimethyl sulfoxide. Chirasil‐Dex, previously formulated exclusively as the O‐6 regioisomer, should be revised as an O‐2‐ and O‐6‐Chirasil‐Dex mixture. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, NMR Spectroscopic Characterization and Polysiloxane‐Based Immobilization of the Three Regioisomeric Monooctenylpermethyl‐β‐cyclodextrins and Their Application in Enantioselective GC

Cousin¹,

Trapp

Peulon-Agasse³

et al. 2003

Eur J Org Chem

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“…Most convenient was the GLC analysis with modified cyclodextrins as chiral stationary phases. [51,52] Alternatively, HPLC analysis with a commercially available column was successful. The absolute configurations were established for most compounds via correlation with known, available reference substances.…”

Section: Cyclopropylmethanolsmentioning

confidence: 99%

Kinetic Enzymatic Resolution of Cyclopropane Derivatives

et al. 2003

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Abstract:The kinetic enzymatic resolution of various cyclopropane derivatives was systematically investigated. The study focused on synthetically useful cyclopropylmethanols (e.g., 18a/j or 19a/j) as well as some rarely investigated cyclopropanols (e.g., 24/25 or 27). The combination of enantioselective catalytic or diastereoselective synthesis of enantiomerically enriched compounds with enzymatic approaches ultimately led to the most convenient route to enantiomerically pure starting materials. Again, this was especially proven for the synthesis of cyclopropanols 18a/j and 19a/j. Key to the successful investigation was to rigorously establish an analytical tool for the analysis of enantiomeric composition of reaction mixtures.

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“…The unique separation properties of b-CD derivatives are mainly attributed to their cavity structures and the electron effects of the derivatization groups. Through the appropriate introduction of a group with special property, it is possible to prepare stationary phases that possess excellent separation ability and chiral recognition for a wide range of analytes, such as Chiralsil-DEX and Chiraldex B-TA [9,10].…”

Section: Introductionmentioning

confidence: 99%

Capillary GC using pyridyl β‐cyclodextrin stationary phase

Shen

Jian

Yang

et al. 2008

J of Separation Science

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A new beta-CD derivative, heptakis [2,6-di-O-pentyl-3-O-(4'-chloro-5'-pyridylmethyl)]-beta-CD, was synthesized by the selective introduction of a pyridyl group on the 3-positions of beta-CD. The chromatographic properties of the pyridyl beta-CD derivative were studied by using it as the stationary phase in capillary GC. The polarity of the prepared stationary phase was moderate, and the separation results demonstrated that the prepared stationary phase possessed excellent separation ability and chiral recognition for a wide range of analytes. Not only the aromatic positional isomers, such as o-, m-, p-xylene and alpha-, beta-naphthol isomers, but also some compounds with multi-stereogenic centers, such as n-(1-methylpropyl)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxamide and n-(1-methylpropyl)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxamide with three stereogenic centers including eight configurational isomers, were successfully separated. The results also indicated that the polarity of the beta-CD derivative, and the hydrogen bonding between the beta-CD derivative, and the analytes had a very important effect on separation.

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Permethyl‐β‐cyclodextrin, Chemically Bonded to Polysiloxane: a Chiral Stationary Phase with Wider Application Range for Enantiomer Separation by Capillary Gas Chromatography

Abstract: be carried out at room temperature because of its thermolability. The crude product obtained (33 YO yield) after work-upt6] and silica gel filtration (CHClJacetone 4/1, subsequent elution of the product with 2-propanol) shows exclusively the molecular peak for a monoglycosidation product

Cited by 83 publications

References 20 publications

Synthesis, NMR Spectroscopic Characterization and Polysiloxane‐Based Immobilization of the Three Regioisomeric Monooctenylpermethyl‐β‐cyclodextrins and Their Application in Enantioselective GC

Synthesis, NMR Spectroscopic Characterization and Polysiloxane‐Based Immobilization of the Three Regioisomeric Monooctenylpermethyl‐β‐cyclodextrins and Their Application in Enantioselective GC

Kinetic Enzymatic Resolution of Cyclopropane Derivatives

Capillary GC using pyridyl β‐cyclodextrin stationary phase

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