%A Wei Chuen Chan
%T Total Synthesis of the Reported Structure of Stresgenin B, its Structural Elucidation Using DFT Calculations, and Visible-Light-Mediated Functionalizations of Electron-Deficient Olefins
%X 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.
%D 2020
%K Total synthesis. Photochemistry. Radical Chemistry.
%I University of Pittsburgh
%L pittir38729