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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
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| 자료유형 | 학위논문 |
|---|---|
| 서명/저자사항 | 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. |
| 개인저자 | Trongsiriwat, Nisalak. |
| 단체저자명 | University of Pennsylvania. Chemistry. |
| 발행사항 | [S.l.]: University of Pennsylvania., 2019. |
| 발행사항 | Ann Arbor: ProQuest Dissertations & Theses, 2019. |
| 형태사항 | 275 p. |
| 기본자료 저록 | Dissertations Abstracts International 81-05B. Dissertation Abstract International |
| ISBN | 9781088366110 |
| 학위논문주기 | Thesis (Ph.D.)--University of Pennsylvania, 2019. |
| 일반주기 |
Source: Dissertations Abstracts International, Volume: 81-05, Section: B.
Advisor: Walsh, Patrick J. |
| 이용제한사항 | This item must not be sold to any third party vendors. |
| 요약 | 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 ---棺,款-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. |
| 일반주제명 | Inorganic chemistry. Organic chemistry. |
| 언어 | 영어 |
| 바로가기 | 
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