Diastereoselective cyclopropanation of medium and large ring alpha, beta-unsaturated homochiral ketals and enantioselective synthesis of (-)-modhephene.

Persistent Link:
http://hdl.handle.net/10150/184664
Title:
Diastereoselective cyclopropanation of medium and large ring alpha, beta-unsaturated homochiral ketals and enantioselective synthesis of (-)-modhephene.
Author:
Math, Shivanand Kumarswamy.
Issue Date:
1989
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:
A general straightforward synthetic approach for the enantioselective construction of medium and large ring cyclopropyl ketones via diastereoselective Simmons-Smith cyclopropanation is discussed. Medium and large 2-cycloalkenone 1,4Di-O-benzyl-L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. The cyclopropyl ketals are obtained in 80-94% with >23:1-8:1 diastereoselectivity. The first enantioselective synthesis of (-)-modhephene, a natural product possessing the carbocyclic (3.3.3) propellane skeleton, by the use of diastereoselective cyclopropanation methodology is described.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Stereochemistry.; Natural products -- Synthesis.; Ketones -- Synthesis.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Mash, Eugene

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleDiastereoselective cyclopropanation of medium and large ring alpha, beta-unsaturated homochiral ketals and enantioselective synthesis of (-)-modhephene.en_US
dc.creatorMath, Shivanand Kumarswamy.en_US
dc.contributor.authorMath, Shivanand Kumarswamy.en_US
dc.date.issued1989en_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.abstractA general straightforward synthetic approach for the enantioselective construction of medium and large ring cyclopropyl ketones via diastereoselective Simmons-Smith cyclopropanation is discussed. Medium and large 2-cycloalkenone 1,4Di-O-benzyl-L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. The cyclopropyl ketals are obtained in 80-94% with >23:1-8:1 diastereoselectivity. The first enantioselective synthesis of (-)-modhephene, a natural product possessing the carbocyclic (3.3.3) propellane skeleton, by the use of diastereoselective cyclopropanation methodology is described.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectStereochemistry.en_US
dc.subjectNatural products -- Synthesis.en_US
dc.subjectKetones -- Synthesis.en_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, Eugeneen_US
dc.contributor.committeememberLaw, Johnen_US
dc.contributor.committeememberBurke, Michaelen_US
dc.contributor.committeememberBates, Roberten_US
dc.contributor.committeememberSteelink, Corneliusen_US
dc.identifier.proquest8915973en_US
dc.identifier.oclc702156085en_US
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