Chan, Wei Chuen
(2020)
Total Synthesis of the Reported Structure of Stresgenin B, its Structural Elucidation Using DFT Calculations, and Visible-Light-Mediated Functionalizations of Electron-Deficient Olefins.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
The first chapter outlines the synthesis of the reported structure of stresgenin B. Stresgenin B was reported to be small molecule inhibitor of heat shock proteins (HSPs). Toward this pursuit, two synthetic routes were investigated. In the first route leading to the undesired diastereomer, the key reaction was a Pummerer rearrangement. In the second route, a neighboring-group directed diastereoselective cyanation is critical for the construction of the fully substituted alpha-amidoketal. A late-stage cerium-mediated alkynylation or Peterson olefination is also crucial in installing the exocyclic olefin. Lastly, computational studies were employed to elucidate the correct structure of stresgenin B. Density Function Theory (DFT) calculations were used to predict the proton (1H) and carbon (13C) nuclear magnetic resonance (NMR) of plausible candidate structures.
In the second chapter, a visible light mediated C–H functionalization of ethers using electron-deficient olefins is reported. 1,3-Dioxolane and 1,3-benzodioxole are suitable reacting partners. A radical-chain mechanism is proposed and corroborated by various experimental proof. DFT calculations suggested that C–H abstraction is the rate-determining step. During the course of the mechanistic studies, alpha-bromomalonate and alpha-bromoester were found to be competent radical initiators.
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| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
8 June 2020 |
| Date Type: |
Publication |
| Defense Date: |
9 March 2020 |
| Approval Date: |
8 June 2020 |
| Submission Date: |
6 April 2020 |
| Access Restriction: |
2 year -- Restrict access to University of Pittsburgh for a period of 2 years. |
| Number of Pages: |
375 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
Total synthesis. Photochemistry. Radical Chemistry. |
| Date Deposited: |
08 Jun 2020 16:00 |
| Last Modified: |
08 Jun 2022 05:15 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/38729 |
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