Diastereoselective cyclopropanation of medium and large ring alpha, beta-unsaturated homochiral ketals and enantioselective synthesis of (-)-modhephene.
| dc.contributor.advisor | Mash, Eugene | en_US |
| dc.contributor.author | Math, Shivanand Kumarswamy. | |
| dc.creator | Math, Shivanand Kumarswamy. | en_US |
| dc.date.accessioned | 2011-10-31T17:14:54Z | |
| dc.date.available | 2011-10-31T17:14:54Z | |
| dc.date.issued | 1989 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10150/184664 | |
| dc.description.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. | |
| dc.language.iso | en | en_US |
| dc.publisher | The University of Arizona. | en_US |
| dc.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. | en_US |
| dc.subject | Stereochemistry. | en_US |
| dc.subject | Natural products -- Synthesis. | en_US |
| dc.subject | Ketones -- Synthesis. | en_US |
| dc.title | Diastereoselective cyclopropanation of medium and large ring alpha, beta-unsaturated homochiral ketals and enantioselective synthesis of (-)-modhephene. | en_US |
| dc.type | text | en_US |
| dc.type | Dissertation-Reproduction (electronic) | en_US |
| dc.identifier.oclc | 702156085 | en_US |
| thesis.degree.grantor | University of Arizona | en_US |
| thesis.degree.level | doctoral | en_US |
| dc.contributor.committeemember | Law, John | en_US |
| dc.contributor.committeemember | Burke, Michael | en_US |
| dc.contributor.committeemember | Bates, Robert | en_US |
| dc.contributor.committeemember | Steelink, Cornelius | en_US |
| dc.identifier.proquest | 8915973 | en_US |
| thesis.degree.discipline | Chemistry | en_US |
| thesis.degree.discipline | Graduate College | en_US |
| thesis.degree.name | Ph.D. | en_US |
| dc.description.note | Digitization note: Original document not clear, scans are faithful to the paper original. | |
| refterms.dateFOA | 2018-08-22T20:13:21Z | |
| html.description.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. |
Files in this item
Name:
azu_td_8915973_sip1_m.pdf
Size:
2.688Mb
Format:
PDF
Description:
azu_td_8915973_sip1_m.pdf