Show simple item record

dc.contributor.advisorMash, Eugene A.en_US
dc.contributor.authorFryling, James Allen.
dc.creatorFryling, James Allen.en_US
dc.date.accessioned2011-10-31T17:34:37Z
dc.date.available2011-10-31T17:34:37Z
dc.date.issued1990en_US
dc.identifier.urihttp://hdl.handle.net/10150/185332
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.
dc.language.isoenen_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.subjectChemistry, Organicen_US
dc.subjectPharmaceutical chemistryen_US
dc.titleEnantiomerically pure acetals in organic synthesis: Resolutions and diastereoselective alkylations of alpha-hydroxy esters.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.identifier.oclc681748140en_US
thesis.degree.grantorUniversity of Arizonaen_US
thesis.degree.leveldoctoralen_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
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.namePh.D.en_US
refterms.dateFOA2018-08-23T02:52:02Z
html.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.


Files in this item

Thumbnail
Name:
azu_td_9117458_sip1_m.pdf
Size:
4.622Mb
Format:
PDF
Description:
azu_td_9117458_sip1_m.pdf

This item appears in the following Collection(s)

Show simple item record