An efficient method for the conversion of versatile beta-keto carbonyl compounds to the corresponding alpha,beta-unsaturated-gamma-oxo carbonyl structural units was developed. This methodology was applied to beta-keto esters, amides and lactones. In most cases generation of the olefinic functionality proceeded with complete E-selectivity. The utility of this chemistry was demonstrated through a formal synthesis of R-(-)-pyrenophorin, an asymmetric total synthesis of (+)-patulolide A and a racemic synthesis of patulolide B. An extensive study of ketal-derived oxonium ylides and the subsequent rearrangement was also accomplished. The application of this chemistry was applied to Bu-2313 and a unique class of compounds known as the hyperolactones.
","abstract_html":"<p>An efficient method for the conversion of versatile beta-keto carbonyl compounds to the corresponding alpha,beta-unsaturated-gamma-oxo carbonyl structural units was developed. This methodology was applied to beta-keto esters, amides and lactones. In most cases generation of the olefinic functionality proceeded with complete E-selectivity. The utility of this chemistry was demonstrated through a formal synthesis of R-(-)-pyrenophorin, an asymmetric total synthesis of (+)-patulolide A and a racemic synthesis of patulolide B. An extensive study of ketal-derived oxonium ylides and the subsequent rearrangement was also accomplished. The application of this chemistry was applied to Bu-2313 and a unique class of compounds known as the hyperolactones.</p>","abstract_has_math":false,"creators":["Ronsheim, Matthew David"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"Dissertation","degree_discipline":null,"degree_department":null,"school":null,"contributors":["Charles K Zercher"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2002,"date_issued":"2002-01-01T08:00:00Z","date_published":"2002-01-01T08:00:00Z","updated_at":"2026-07-24T05:21:54Z","subjects":["Chemistry","Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholars.unh.edu/dissertation/93","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Charles K Zercher"]},{"key":"dc:creator","label":"Author","values":["Ronsheim, Matthew David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholars.unh.edu/dissertation/93"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["An efficient method for the conversion of versatile beta-keto carbonyl compounds to the corresponding alpha,beta-unsaturated-gamma-oxo carbonyl structural units was developed. This methodology was applied to beta-keto esters, amides and lactones. In most cases generation of the olefinic functionality proceeded with complete E-selectivity. The utility of this chemistry was demonstrated through a formal synthesis of R-(-)-pyrenophorin, an asymmetric total synthesis of (+)-patulolide A and a racemic synthesis of patulolide B. An extensive study of ketal-derived oxonium ylides and the subsequent rearrangement was also accomplished. The application of this chemistry was applied to Bu-2313 and a unique class of compounds known as the hyperolactones.
"]},{"key":"dc:title","label":"Title","values":["A facile conversion of beta-keto carbonyl compounds to alpha, beta-unsaturated-gamma-oxo carbonyl systems and a study of ketal -derived oxonium ylides"]}]}],"canonical_facts":{"dc:contributor":["Charles K Zercher"],"dc:creator":["Ronsheim, Matthew David"],"dc:description.abstract":["An efficient method for the conversion of versatile beta-keto carbonyl compounds to the corresponding alpha,beta-unsaturated-gamma-oxo carbonyl structural units was developed. This methodology was applied to beta-keto esters, amides and lactones. In most cases generation of the olefinic functionality proceeded with complete E-selectivity. The utility of this chemistry was demonstrated through a formal synthesis of R-(-)-pyrenophorin, an asymmetric total synthesis of (+)-patulolide A and a racemic synthesis of patulolide B. An extensive study of ketal-derived oxonium ylides and the subsequent rearrangement was also accomplished. The application of this chemistry was applied to Bu-2313 and a unique class of compounds known as the hyperolactones.
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