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Total Synthesis of the Reported Structure of Stresgenin B, its Structural Elucidation Using DFT Calculations, and Visible-Light-Mediated Functionalizations of Electron-Deficient Olefins

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 (Unpublished)

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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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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Chan, Wei Chuenwlc12@pitt.eduWLC120000-0003-0199-8960
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairKoide, Kazunorikoide@pitt.edu
Committee MemberFloreancig, Paulflorean@pitt.edu
Committee MemberWipf, Peterpwipf@pitt.edu
Committee MemberBrodsky, Jeffreyjbrodsky@pitt.edu
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 2020 16:00
URI: http://d-scholarship.pitt.edu/id/eprint/38729

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