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Intramolecular [4+2] cycloadditions of conjugated ynones and related species ; Studies directed toward the total systhesis of glycinoeclepin A

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dc.contributor.advisor Rick L. Danheiser. en_US Diffendal, Jason Michael, 1975- en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US 2005-05-19T15:10:22Z 2005-05-19T15:10:22Z 2002 en_US 2002 en_US
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2002. en_US
dc.description Includes bibliographical references. en_US
dc.description This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. en_US
dc.description.abstract The intramolecular [4 + 2] cycloaddition reactions of c,-alkynyl carbonyl compounds are described. This reaction, the first heterocyclic variant of the enyne cycloaddition reaction, affords a product with a dihydroisobenzofuran ring system. For this reaction, we propose a mechanism in which a highly strained heterocyclic allene intermediate undergoes an unusual rearrangement leading to a 3-furfuryl carbene. A 1,2-C-H insertion then produces the polycyclic furan product. A detailed analysis of the scope and mechanism of this reaction is presented. The synthetic utility of the method for the synthesis of complex organic molecules is illustrated by two sequences demonstraing further transformations of the dihydroisobenzofuran products. A two-step formal benzannulation process generates a tetrahydroanthracene derivative. Ozonolysis of a 7-oxabicycloheptene derivative prepared from a dihydroisobenzofuran affords a product that contains the core oxabicyclo[6.2.1]undecane ring system of eleutherobin and the sarcodictyin family of natural products. Glycinoeclepin A is the natural hatching stimulus agent of the soybean cystnematode. A new strategy for the synthesis of an advanced A-ring intermediate in the total synthesis of this important compound is presented. This strategy provides the key A-ring enyne intermediate in seven steps from 2,2-dimethylcyclohexanedione, utilizing a novel acid-catalyzed cyclization reaction of a hydroxy enedione. en_US
dc.description.statementofresponsibility by Jason Michael Diffendal. en_US
dc.format.extent 282 leaves en_US
dc.format.extent 17543079 bytes
dc.format.extent 17542830 bytes
dc.format.mimetype application/pdf
dc.format.mimetype application/pdf
dc.language.iso eng en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. en_US
dc.subject Chemistry. en_US
dc.title Intramolecular [4+2] cycloadditions of conjugated ynones and related species ; Studies directed toward the total systhesis of glycinoeclepin A en_US
dc.type Thesis en_US Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 51956193 en_US

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