Enantiomerically pure acetals in organic synthesis: Resolutions and diastereoselective alkylations of alpha-hydroxy esters.

Persistent Link:
http://hdl.handle.net/10150/185332
Title:
Enantiomerically pure acetals in organic synthesis: Resolutions and diastereoselective alkylations of alpha-hydroxy esters.
Author:
Fryling, James Allen.
Issue Date:
1990
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
The diastereomeric tetrahydropyranyl (THP) and tetrahydrofuranyl (THF) ethers of a variety of α-hydroxyesters were synthesized and separated by column chromatography. The separability of the diastereomers was found to be a general phenomenon which allowed for wide variations in both the THP/THF ring and the α-hydroxyester. The resolved compounds could be deprotonated and alkylated diastereoselectively with a variety of electrophiles. The diastereoselectivity ranged from 1:1 to 12:1 depending on the α-hydroxyester, the alkylating agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This alkylation method was used in the synthesis of the natural product (S)-frontalin and its enantiomer with optical purity. Modifications to the THP and THF rings were synthesized in an attempt to develop a "chiral THP". The (S)-methyl lactyl, (S)-methyl mandelyl, and (R)-pantolactyl 3-benzyloxytetrahydrofuranosides were synthesized and separated. Transacetalization to the methyl furanosides gave "chiral THF's" which were used in the resolution of other racemic α-hydroxyesters.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry, Organic; Pharmaceutical chemistry
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Mash, Eugene A.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleEnantiomerically pure acetals in organic synthesis: Resolutions and diastereoselective alkylations of alpha-hydroxy esters.en_US
dc.creatorFryling, James Allen.en_US
dc.contributor.authorFryling, James Allen.en_US
dc.date.issued1990en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThe diastereomeric tetrahydropyranyl (THP) and tetrahydrofuranyl (THF) ethers of a variety of α-hydroxyesters were synthesized and separated by column chromatography. The separability of the diastereomers was found to be a general phenomenon which allowed for wide variations in both the THP/THF ring and the α-hydroxyester. The resolved compounds could be deprotonated and alkylated diastereoselectively with a variety of electrophiles. The diastereoselectivity ranged from 1:1 to 12:1 depending on the α-hydroxyester, the alkylating agent, and the reaction conditions. In most cases the diastereomeric products of the alkylation were also separated by column chromatography. This alkylation method was used in the synthesis of the natural product (S)-frontalin and its enantiomer with optical purity. Modifications to the THP and THF rings were synthesized in an attempt to develop a "chiral THP". The (S)-methyl lactyl, (S)-methyl mandelyl, and (R)-pantolactyl 3-benzyloxytetrahydrofuranosides were synthesized and separated. Transacetalization to the methyl furanosides gave "chiral THF's" which were used in the resolution of other racemic α-hydroxyesters.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry, Organicen_US
dc.subjectPharmaceutical chemistryen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorMash, Eugene A.en_US
dc.contributor.committeememberMulvaney, James E.en_US
dc.contributor.committeememberBates, Robert B.en_US
dc.contributor.committeememberBurke, Michael F.en_US
dc.contributor.committeememberWigley, David E.en_US
dc.identifier.proquest9117458en_US
dc.identifier.oclc681748140en_US
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