{"id":{"repo_id":"maryland","oai_identifier":"oai:drum.lib.umd.edu:1903/15683"},"canonical_url":"https://search.dev.ndltd.org/etd/maryland/oai:drum.lib.umd.edu:1903/15683","repository":{"repo_id":"maryland","name":"University of Maryland","base_url":"https://api.drum.lib.umd.edu/server/oai/request"},"display":{"title":"Applications of 2,3-Diketoesters in Organic Synthesis and Stereoselective Transformations","abstract":"Dimethyldioxyrane oxidation of δ-hydroxy-α-diazo-β-ketoesters that are prepared by zinc triflate catalyzed Mukaiyama-aldol condensation of methyl diazoacetoacetates with aldehydes, occurred in quantitative yield to form dihydrofuranols that undergo acid catalyzed dehydration under mild conditions to generate 3-methoxyfuran-2-carboxylates in good yield. Oxidation of ζ-keto-α-diazo-β-ketoesters that are formed by zinc triflate catalyzed Mukaiyama-Michael condensation of methyl diazoacetoacetate enones procduced their 2,3,7-diketoester derivative in quantitative yield. The intramolecular acid catalyzed aldol cyclization of 2,3,7-triketoesters provides highly functionalized cyclopentanones with good diastereoselectivity in high overall yields via kinetically controlled and stereodivergent catalytic processes. Lewis acid catalysis gives high selectivity for the 1,3-anti tetrasubstituted cyclopentanones, whereas Brønsted acid catalysis produces the corresponding 1,3-syn diastereomer. The first enantioselective transformation of 2,3-diketoesters was demonstrated in carbonyl-ene reactions catalyzed by [Cu((S,S)-tert-Bu-box)](SbF6)2 generating chiral α-functionalized-α-hydroxy-β-ketoesters in up to 94% yield and 97% ee. The suggested mode of activation is bi-dentate coordination between copper and the oxygen atoms of the two keto-carbonyl groups. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and catalyst loading as low as 1.0 mol % is achieved.","abstract_html":"Dimethyldioxyrane oxidation of δ-hydroxy-α-diazo-β-ketoesters that are prepared by zinc triflate catalyzed Mukaiyama-aldol condensation of methyl diazoacetoacetates with aldehydes, occurred in quantitative yield to form dihydrofuranols that undergo acid catalyzed dehydration under mild conditions to generate 3-methoxyfuran-2-carboxylates in good yield. Oxidation of ζ-keto-α-diazo-β-ketoesters that are formed by zinc triflate catalyzed Mukaiyama-Michael condensation of methyl diazoacetoacetate enones procduced their 2,3,7-diketoester derivative in quantitative yield. The intramolecular acid catalyzed aldol cyclization of 2,3,7-triketoesters provides highly functionalized cyclopentanones with good diastereoselectivity in high overall yields via kinetically controlled and stereodivergent catalytic processes. Lewis acid catalysis gives high selectivity for the 1,3-anti tetrasubstituted cyclopentanones, whereas Brønsted acid catalysis produces the corresponding 1,3-syn diastereomer. The first enantioselective transformation of 2,3-diketoesters was demonstrated in carbonyl-ene reactions catalyzed by [Cu((S,S)-tert-Bu-box)](SbF6)2 generating chiral α-functionalized-α-hydroxy-β-ketoesters in up to 94% yield and 97% ee. The suggested mode of activation is bi-dentate coordination between copper and the oxygen atoms of the two keto-carbonyl groups. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and catalyst loading as low as 1.0 mol % is achieved.","abstract_has_math":false,"creators":["Truong, Phong Minh"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":["Doyle, Michael P"],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014","date_published":"2014","updated_at":"2026-07-24T03:02:27Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.13016/M2FS3R"],"render_values":[{"text":"https://doi.org/10.13016/M2FS3R","href":"https://doi.org/10.13016/M2FS3R","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/1903/15683","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Doyle, Michael P"]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Truong, Phong Minh"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-10-11T05:34:17Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-10-11T05:34:17Z"]},{"key":"dc:date.issued","label":"Date","values":["2014"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.13016/M2FS3R"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1903/15683"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Dimethyldioxyrane oxidation of δ-hydroxy-α-diazo-β-ketoesters that are prepared by zinc triflate catalyzed Mukaiyama-aldol condensation of methyl diazoacetoacetates with aldehydes, occurred in quantitative yield to form dihydrofuranols that undergo acid catalyzed dehydration under mild conditions to generate 3-methoxyfuran-2-carboxylates in good yield. Oxidation of ζ-keto-α-diazo-β-ketoesters that are formed by zinc triflate catalyzed Mukaiyama-Michael condensation of methyl diazoacetoacetate enones procduced their 2,3,7-diketoester derivative in quantitative yield. The intramolecular acid catalyzed aldol cyclization of 2,3,7-triketoesters provides highly functionalized cyclopentanones with good diastereoselectivity in high overall yields via kinetically controlled and stereodivergent catalytic processes. Lewis acid catalysis gives high selectivity for the 1,3-anti tetrasubstituted cyclopentanones, whereas Brønsted acid catalysis produces the corresponding 1,3-syn diastereomer. The first enantioselective transformation of 2,3-diketoesters was demonstrated in carbonyl-ene reactions catalyzed by [Cu((S,S)-tert-Bu-box)](SbF6)2 generating chiral α-functionalized-α-hydroxy-β-ketoesters in up to 94% yield and 97% ee. The suggested mode of activation is bi-dentate coordination between copper and the oxygen atoms of the two keto-carbonyl groups. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and catalyst loading as low as 1.0 mol % is achieved."]},{"key":"dc:title","label":"Title","values":["Applications of 2,3-Diketoesters in Organic Synthesis and Stereoselective Transformations"]}]}],"canonical_facts":{"dc:contributor.advisor":["Doyle, Michael P"],"dc:contributor.department":["Chemistry"],"dc:creator":["Truong, Phong Minh"],"dc:date.accessioned":["2014-10-11T05:34:17Z"],"dc:date.available":["2014-10-11T05:34:17Z"],"dc:date.issued":["2014"],"dc:description.abstract":["Dimethyldioxyrane oxidation of δ-hydroxy-α-diazo-β-ketoesters that are prepared by zinc triflate catalyzed Mukaiyama-aldol condensation of methyl diazoacetoacetates with aldehydes, occurred in quantitative yield to form dihydrofuranols that undergo acid catalyzed dehydration under mild conditions to generate 3-methoxyfuran-2-carboxylates in good yield. Oxidation of ζ-keto-α-diazo-β-ketoesters that are formed by zinc triflate catalyzed Mukaiyama-Michael condensation of methyl diazoacetoacetate enones procduced their 2,3,7-diketoester derivative in quantitative yield. The intramolecular acid catalyzed aldol cyclization of 2,3,7-triketoesters provides highly functionalized cyclopentanones with good diastereoselectivity in high overall yields via kinetically controlled and stereodivergent catalytic processes. Lewis acid catalysis gives high selectivity for the 1,3-anti tetrasubstituted cyclopentanones, whereas Brønsted acid catalysis produces the corresponding 1,3-syn diastereomer. The first enantioselective transformation of 2,3-diketoesters was demonstrated in carbonyl-ene reactions catalyzed by [Cu((S,S)-tert-Bu-box)](SbF6)2 generating chiral α-functionalized-α-hydroxy-β-ketoesters in up to 94% yield and 97% ee. The suggested mode of activation is bi-dentate coordination between copper and the oxygen atoms of the two keto-carbonyl groups. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and catalyst loading as low as 1.0 mol % is achieved."],"dc:identifier":["https://doi.org/10.13016/M2FS3R"],"dc:identifier.uri":["http://hdl.handle.net/1903/15683"],"dc:language.iso":["en"],"dc:title":["Applications of 2,3-Diketoesters in Organic Synthesis and Stereoselective Transformations"],"dc:type":["Dissertation"]},"updated_at":"2026-07-24T03:02:27Z"}