{"id":{"repo_id":"penn","oai_identifier":"oai:repository.upenn.edu:20.500.14332/30533"},"canonical_url":"https://search.dev.ndltd.org/etd/penn/oai:repository.upenn.edu:20.500.14332/30533","repository":{"repo_id":"penn","name":"University of Pennsylvania","base_url":"https://repository.upenn.edu/server/oai/request"},"display":{"title":"Part I: The Study Of 2-Aryl-1,3-Dithiane Derivatives As Pronucleophiles In Palladium-Catalyzed Allylic Alkylation And Propellylation Part Ii: Ligand-Free Palladium-Catalyzed Allylic Amintion Of Hydrazone Derivatives Part Iii: Synthesis Of Criegee Intermediate Precursors","abstract":"Chapter 1 and 2 detail studies of 2-aryl-1,3-dithianes as pronucleophiles in palladium-catalyzed allylic alkylation and propellylation to access skeletally diverse aryl alkyl ketone cores. Allylic carbonate and [1.1.1]propellane electrophiles successfully couple with in situ generated 2-sodio-1,3-dithiane nucleophiles to afford the corresponding products in good to excellent yields. Deprotection of these products leads to valuable aryl alkyl ketones. The palladium-catalyzed allylic alkylation of 2-aryl-1,3-dithianes is examined in chapter 1. A direct synthesis of unsaturated ketones via a one-pot allylation-oxidation protocol is also presented. Additionally, the utility of this method is demonstrated through a sequential one-pot allylation-Heck cyclization to produce asterogynin derivatives which are important bioactive compounds in medicinal chemistry. Chapter 2 discloses a general method for the synthesis of bicyclo[1.1.1]pentane (BCP)-containing dithianes which, upon deprotection, provide access to BCP analogues of medicinally abundant diarylketones. Transformation of the dithiane part into a variety of functional groups such as BCP aryl difluoromethanes and BCP esteare demonstrated. A computational study indicates that the reaction of 2-aryl-1,3-dithianes and [1.1.1]propellane proceeds via a two-electron pathway. Chapter 3 focuses on a protocol for ligand-free palladium catalyzed allylic amination of in situ generated hydrazone nucleophiles at room temperature. This method is effective and applicable for a variety of hydrazones in excellent yields and also economical due to low palladium loading and ligand-free conditions. In addition, we demonstrated an example of tandem allylation-Fischer indole cyclization to afford the core structure of antifungal drug. In chapter 4, we introduce detailed on novel synthesis of (Z/E)-1,3-diiodobut-2-ene and (E)-1,3-diiodo-2-methylprop-1-ene which are considered as precursors of Criegee intermediates methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MARC-oxide) respectively.","abstract_html":"Chapter 1 and 2 detail studies of 2-aryl-1,3-dithianes as pronucleophiles in palladium-catalyzed allylic alkylation and propellylation to access skeletally diverse aryl alkyl ketone cores. Allylic carbonate and [1.1.1]propellane electrophiles successfully couple with in situ generated 2-sodio-1,3-dithiane nucleophiles to afford the corresponding products in good to excellent yields. Deprotection of these products leads to valuable aryl alkyl ketones. The palladium-catalyzed allylic alkylation of 2-aryl-1,3-dithianes is examined in chapter 1. A direct synthesis of unsaturated ketones via a one-pot allylation-oxidation protocol is also presented. Additionally, the utility of this method is demonstrated through a sequential one-pot allylation-Heck cyclization to produce asterogynin derivatives which are important bioactive compounds in medicinal chemistry. Chapter 2 discloses a general method for the synthesis of bicyclo[1.1.1]pentane (BCP)-containing dithianes which, upon deprotection, provide access to BCP analogues of medicinally abundant diarylketones. Transformation of the dithiane part into a variety of functional groups such as BCP aryl difluoromethanes and BCP esteare demonstrated. A computational study indicates that the reaction of 2-aryl-1,3-dithianes and [1.1.1]propellane proceeds via a two-electron pathway. Chapter 3 focuses on a protocol for ligand-free palladium catalyzed allylic amination of in situ generated hydrazone nucleophiles at room temperature. This method is effective and applicable for a variety of hydrazones in excellent yields and also economical due to low palladium loading and ligand-free conditions. In addition, we demonstrated an example of tandem allylation-Fischer indole cyclization to afford the core structure of antifungal drug. In chapter 4, we introduce detailed on novel synthesis of (Z/E)-1,3-diiodobut-2-ene and (E)-1,3-diiodo-2-methylprop-1-ene which are considered as precursors of Criegee intermediates methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MARC-oxide) respectively.","abstract_has_math":false,"creators":["Trongsiriwat, Nisalak"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Patrick J. Walsh"],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019","date_published":"2019","updated_at":"2026-07-24T03:47:17Z","subjects":[],"languages":["en"],"rights":["Nisalak Trongsiriwat"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://repository.upenn.edu/handle/20.500.14332/30533","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Patrick J. 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Allylic carbonate and [1.1.1]propellane electrophiles successfully couple with in situ generated 2-sodio-1,3-dithiane nucleophiles to afford the corresponding products in good to excellent yields. Deprotection of these products leads to valuable aryl alkyl ketones. The palladium-catalyzed allylic alkylation of 2-aryl-1,3-dithianes is examined in chapter 1. A direct synthesis of unsaturated ketones via a one-pot allylation-oxidation protocol is also presented. Additionally, the utility of this method is demonstrated through a sequential one-pot allylation-Heck cyclization to produce asterogynin derivatives which are important bioactive compounds in medicinal chemistry. Chapter 2 discloses a general method for the synthesis of bicyclo[1.1.1]pentane (BCP)-containing dithianes which, upon deprotection, provide access to BCP analogues of medicinally abundant diarylketones. Transformation of the dithiane part into a variety of functional groups such as BCP aryl difluoromethanes and BCP esteare demonstrated. A computational study indicates that the reaction of 2-aryl-1,3-dithianes and [1.1.1]propellane proceeds via a two-electron pathway. Chapter 3 focuses on a protocol for ligand-free palladium catalyzed allylic amination of in situ generated hydrazone nucleophiles at room temperature. This method is effective and applicable for a variety of hydrazones in excellent yields and also economical due to low palladium loading and ligand-free conditions. In addition, we demonstrated an example of tandem allylation-Fischer indole cyclization to afford the core structure of antifungal drug. In chapter 4, we introduce detailed on novel synthesis of (Z/E)-1,3-diiodobut-2-ene and (E)-1,3-diiodo-2-methylprop-1-ene which are considered as precursors of Criegee intermediates methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MARC-oxide) respectively."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Doctor of Philosophy (PhD)"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Part I: The Study Of 2-Aryl-1,3-Dithiane Derivatives As Pronucleophiles In Palladium-Catalyzed Allylic Alkylation And Propellylation Part Ii: Ligand-Free Palladium-Catalyzed Allylic Amintion Of Hydrazone Derivatives Part Iii: Synthesis Of Criegee Intermediate Precursors"]}]}],"canonical_facts":{"dc:contributor.advisor":["Patrick J. Walsh"],"dc:creator":["Trongsiriwat, Nisalak"],"dc:date":["2023-05-17T22:58:56.000"],"dc:date.accessioned":["2023-05-22T17:43:15Z"],"dc:date.available":["2001-01-01T00:00:00Z"],"dc:date.issued":["2019"],"dc:description.abstract":["Chapter 1 and 2 detail studies of 2-aryl-1,3-dithianes as pronucleophiles in palladium-catalyzed allylic alkylation and propellylation to access skeletally diverse aryl alkyl ketone cores. Allylic carbonate and [1.1.1]propellane electrophiles successfully couple with in situ generated 2-sodio-1,3-dithiane nucleophiles to afford the corresponding products in good to excellent yields. Deprotection of these products leads to valuable aryl alkyl ketones. The palladium-catalyzed allylic alkylation of 2-aryl-1,3-dithianes is examined in chapter 1. A direct synthesis of unsaturated ketones via a one-pot allylation-oxidation protocol is also presented. Additionally, the utility of this method is demonstrated through a sequential one-pot allylation-Heck cyclization to produce asterogynin derivatives which are important bioactive compounds in medicinal chemistry. Chapter 2 discloses a general method for the synthesis of bicyclo[1.1.1]pentane (BCP)-containing dithianes which, upon deprotection, provide access to BCP analogues of medicinally abundant diarylketones. Transformation of the dithiane part into a variety of functional groups such as BCP aryl difluoromethanes and BCP esteare demonstrated. A computational study indicates that the reaction of 2-aryl-1,3-dithianes and [1.1.1]propellane proceeds via a two-electron pathway. Chapter 3 focuses on a protocol for ligand-free palladium catalyzed allylic amination of in situ generated hydrazone nucleophiles at room temperature. This method is effective and applicable for a variety of hydrazones in excellent yields and also economical due to low palladium loading and ligand-free conditions. In addition, we demonstrated an example of tandem allylation-Fischer indole cyclization to afford the core structure of antifungal drug. In chapter 4, we introduce detailed on novel synthesis of (Z/E)-1,3-diiodobut-2-ene and (E)-1,3-diiodo-2-methylprop-1-ene which are considered as precursors of Criegee intermediates methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MARC-oxide) respectively."],"dc:description.degree":["Doctor of Philosophy (PhD)"],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["https://repository.upenn.edu/handle/20.500.14332/30533"],"dc:language":["en"],"dc:rights":["Nisalak Trongsiriwat"],"dc:title":["Part I: The Study Of 2-Aryl-1,3-Dithiane Derivatives As Pronucleophiles In Palladium-Catalyzed Allylic Alkylation And Propellylation Part Ii: Ligand-Free Palladium-Catalyzed Allylic Amintion Of Hydrazone Derivatives Part Iii: Synthesis Of Criegee Intermediate Precursors"],"dc:type":["Dissertation/Thesis"]},"updated_at":"2026-07-24T03:47:17Z"}