{"id":{"repo_id":"byu","oai_identifier":"oai:scholarsarchive.byu.edu:etd-2414"},"canonical_url":"https://search.dev.ndltd.org/etd/byu/oai:scholarsarchive.byu.edu:etd-2414","repository":{"repo_id":"byu","name":"Brigham Young University","base_url":"https://scholarsarchive.byu.edu/do/oai/"},"display":{"title":"Synthesis of Resveratrol and Its Analogs, Phase-Transfer Catalyzed Asymmetric Glycolate Aldol Reaction, and Total Synthesis of 8,9-Methylamido-Geldanamycin","abstract":"The phytoalexin resveratrol and its acetyl analogs have been made using a decarbonylative Heck reaction. The acid chloride derived from 3,5-dihydroxybenzoic acid was coupled with suitable protected 4-hydroxystyrene in the presence of palladium acetate and N,N-bis-(2,6-diisopropylphenyl)-4,5-dihydro imidazolium chloride to give the substituted stilbene in good yield as the key step. Human HL-60 cell assays showed the 4'-acetyl resveratrol variant improved activity (ED50 17 μM) relative to resveratrol (24 μM). Cinchona phase-transfer catalysts (PTC) were developed for glycolate aldol reactions to give differentially protected 1,2-diol products. Silyl enol ether of diphenylmethoxy-2,5-dimethoxyacetophenone reacted to generate benzhydryl-protected products. O-Allyl trifluorobenzyl cinchonium hydrodifluoride (20 mol %) catalyzed the addition of the silyl enol ether to benzaldehyde to give aldol product as a single syn-product in 76% yield and 80% ee. Recrystallization enriched the product to 95% ee, and a Baeyer-Villiger reaction transformed the product into useful ester intermediates. A novel unnatural product, 8,9-Methylamido-Geldanamycin, has been designed and synthesized. Using a convergent route, the total synthesis of the molecule involved only 27 longest linear steps. New synthesis methodologies, including auxiliary controlled asymmetric anti-glycolate aldol, syn-norephedrine aldol, and selective p-quinone formation, were used.","abstract_html":"The phytoalexin resveratrol and its acetyl analogs have been made using a decarbonylative Heck reaction. The acid chloride derived from 3,5-dihydroxybenzoic acid was coupled with suitable protected 4-hydroxystyrene in the presence of palladium acetate and N,N-bis-(2,6-diisopropylphenyl)-4,5-dihydro imidazolium chloride to give the substituted stilbene in good yield as the key step. Human HL-60 cell assays showed the 4'-acetyl resveratrol variant improved activity (ED50 17 μM) relative to resveratrol (24 μM). Cinchona phase-transfer catalysts (PTC) were developed for glycolate aldol reactions to give differentially protected 1,2-diol products. Silyl enol ether of diphenylmethoxy-2,5-dimethoxyacetophenone reacted to generate benzhydryl-protected products. O-Allyl trifluorobenzyl cinchonium hydrodifluoride (20 mol %) catalyzed the addition of the silyl enol ether to benzaldehyde to give aldol product as a single syn-product in 76% yield and 80% ee. Recrystallization enriched the product to 95% ee, and a Baeyer-Villiger reaction transformed the product into useful ester intermediates. A novel unnatural product, 8,9-Methylamido-Geldanamycin, has been designed and synthesized. Using a convergent route, the total synthesis of the molecule involved only 27 longest linear steps. New synthesis methodologies, including auxiliary controlled asymmetric anti-glycolate aldol, syn-norephedrine aldol, and selective p-quinone formation, were used.","abstract_has_math":false,"creators":["Liu, Jing"],"institution":"Brigham Young University - Provo","degree_name":"PhD","degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":null,"date_issued":"","date_published":null,"updated_at":"2026-07-24T01:29:12Z","subjects":["resveratrol","phase-transfer catalysts","aldol","Geldanamycin","decarbonylative Heck reaction.","Biochemistry","Chemistry"],"languages":["English"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholarsarchive.byu.edu/etd/1415","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Liu, Jing"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2007-07-16T07:00:00Z"]},{"key":"dc:publisher","label":"Institution","values":["Brigham Young University - Provo"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["PhD"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["resveratrol","phase-transfer catalysts","aldol","Geldanamycin","decarbonylative Heck reaction.","Biochemistry","Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://scholarsarchive.byu.edu/etd/1415","https://scholarsarchive.byu.edu/context/etd/article/2414/viewcontent/ETD_CISOPTR_1419.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Physical and Mathematical Sciences; Chemistry and Biochemistry"]},{"key":"dc:description.abstract","label":"Abstract","values":["The phytoalexin resveratrol and its acetyl analogs have been made using a decarbonylative Heck reaction. The acid chloride derived from 3,5-dihydroxybenzoic acid was coupled with suitable protected 4-hydroxystyrene in the presence of palladium acetate and N,N-bis-(2,6-diisopropylphenyl)-4,5-dihydro imidazolium chloride to give the substituted stilbene in good yield as the key step. Human HL-60 cell assays showed the 4'-acetyl resveratrol variant improved activity (ED50 17 μM) relative to resveratrol (24 μM). Cinchona phase-transfer catalysts (PTC) were developed for glycolate aldol reactions to give differentially protected 1,2-diol products. Silyl enol ether of diphenylmethoxy-2,5-dimethoxyacetophenone reacted to generate benzhydryl-protected products. O-Allyl trifluorobenzyl cinchonium hydrodifluoride (20 mol %) catalyzed the addition of the silyl enol ether to benzaldehyde to give aldol product as a single syn-product in 76% yield and 80% ee. Recrystallization enriched the product to 95% ee, and a Baeyer-Villiger reaction transformed the product into useful ester intermediates. A novel unnatural product, 8,9-Methylamido-Geldanamycin, has been designed and synthesized. Using a convergent route, the total synthesis of the molecule involved only 27 longest linear steps. New synthesis methodologies, including auxiliary controlled asymmetric anti-glycolate aldol, syn-norephedrine aldol, and selective p-quinone formation, were used."]},{"key":"dc:format","label":"Dc Format","values":["application:pdf"]},{"key":"dc:source","label":"Dc Source","values":["Brigham Young University - Provo"]},{"key":"dc:title","label":"Title","values":["Synthesis of Resveratrol and Its Analogs, Phase-Transfer Catalyzed Asymmetric Glycolate Aldol Reaction, and Total Synthesis of 8,9-Methylamido-Geldanamycin"]}]}],"canonical_facts":{"dc:creator":["Liu, Jing"],"dc:date":["2007-07-16T07:00:00Z"],"dc:description":["Physical and Mathematical Sciences; Chemistry and Biochemistry"],"dc:description.abstract":["The phytoalexin resveratrol and its acetyl analogs have been made using a decarbonylative Heck reaction. The acid chloride derived from 3,5-dihydroxybenzoic acid was coupled with suitable protected 4-hydroxystyrene in the presence of palladium acetate and N,N-bis-(2,6-diisopropylphenyl)-4,5-dihydro imidazolium chloride to give the substituted stilbene in good yield as the key step. Human HL-60 cell assays showed the 4'-acetyl resveratrol variant improved activity (ED50 17 μM) relative to resveratrol (24 μM). Cinchona phase-transfer catalysts (PTC) were developed for glycolate aldol reactions to give differentially protected 1,2-diol products. Silyl enol ether of diphenylmethoxy-2,5-dimethoxyacetophenone reacted to generate benzhydryl-protected products. O-Allyl trifluorobenzyl cinchonium hydrodifluoride (20 mol %) catalyzed the addition of the silyl enol ether to benzaldehyde to give aldol product as a single syn-product in 76% yield and 80% ee. Recrystallization enriched the product to 95% ee, and a Baeyer-Villiger reaction transformed the product into useful ester intermediates. A novel unnatural product, 8,9-Methylamido-Geldanamycin, has been designed and synthesized. Using a convergent route, the total synthesis of the molecule involved only 27 longest linear steps. New synthesis methodologies, including auxiliary controlled asymmetric anti-glycolate aldol, syn-norephedrine aldol, and selective p-quinone formation, were used."],"dc:format":["application:pdf"],"dc:identifier":["https://scholarsarchive.byu.edu/etd/1415","https://scholarsarchive.byu.edu/context/etd/article/2414/viewcontent/ETD_CISOPTR_1419.pdf"],"dc:language":["English"],"dc:publisher":["Brigham Young University - Provo"],"dc:source":["Brigham Young University - Provo"],"dc:subject":["resveratrol","phase-transfer catalysts","aldol","Geldanamycin","decarbonylative Heck reaction.","Biochemistry","Chemistry"],"dc:title":["Synthesis of Resveratrol and Its Analogs, Phase-Transfer Catalyzed Asymmetric Glycolate Aldol Reaction, and Total Synthesis of 8,9-Methylamido-Geldanamycin"],"dc:type":["Dissertation"],"thesis:degree_name":["PhD"]},"updated_at":"2026-07-24T01:29:12Z"}