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Pericyclic reactions in organic synthesis

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dc.contributor.advisor Rick L. Danheiser. en_US Robinson-Surry, Julia M. (Julia Mae) en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US 2011-08-18T19:11:49Z 2011-08-18T19:11:49Z 2011 en_US 2011 en_US
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011. en_US
dc.description Page 147 missing. Cataloged from PDF version of thesis. en_US
dc.description Includes bibliographical references. en_US
dc.description.abstract Part I of this thesis describes a formal, metal-free, [2 + 2 + 2] cycloaddition strategy based on a cascade of two pericyclic processes. An intramolecular propargylic ene reaction of a 1,6-diyne is used to generate a vinylallene, which then reacts in an inter- or intramolecular Diels-Alder reaction with an alkenyl or alkynyl dienophile. Reactions involving unsymmetrical alkenyl and alkynyl dienophiles proceed with good to excellent regioselectivity, and endo products are formed exclusively. The mechanism of several earlier fully intramolecular related transformations have been shown to involve an analogous process rather than the diradicalmediated pathways proposed previously. Part II of this thesis describes a [4 + 4] annulation strategy involving the intramolecular [4 + 2] cycloaddition of conjugated enynes with activated cyclobutene derivatives to access intermediates containing bicyclo[4.2.0]-2,4-octadiene moieties that then undergo electrocyclic ring opening reactions to provide 1,3,5-cyclooctatrienes. Five novel cyclooctatrienes have been prepared using this method. Part III of this thesis describes the use of supercritical carbon dioxide as an environmentally friendly alternative to conventional solvents for the synthesis of a variety of carboxylic amides. The addition of amines to ketenes generated in situ via the retro-ene reaction of alkynyl ethers provides amides in good yield, in many cases with ethylene as the only byproduct of the reaction. With the exception of primary, unbranched amines, potential side reactions involving addition of the amines to carbon dioxide are not competitive with the desired C-N bond-forming reaction. The amide synthesis is applicable to the preparation of p-hydroxy and P-amino amide derivatives, as well as amides bearing isolated carbon-carbon double bonds. en_US
dc.description.statementofresponsibility by Julia M. Robinson-Surry. en_US
dc.format.extent 328 p. en_US
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.rights.uri en_US
dc.subject Chemistry. en_US
dc.title Pericyclic reactions in organic synthesis 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 743793114 en_US

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