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Browsing by Author "Jin, Mengyuan"

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    Silicon Chemistry in Prodrug Strategy and Polymer Design And Intermolecular HDDA Chemistry
    (2023-04) Jin, Mengyuan
    This document will include four chapters, each talking about one of the projects that I’ve been working on. Chapter I features my contribution to the silicate prodrug project of anticancer drug paclitaxel (PTX). The Hoye group developed the silicate prodrug strategy to realize controlled release of the parent drug, PTX, in vivo/vitro. The results showed well controlled hydrolysis rate under acidic aqueous condition through varying the dangling groups on silicon atom. However, the silicate functional groups added hydrophobicity to the drug molecule, imposing difficulty on drug delivery. I specifically explored the possibility of attaching hydrophilic polyethylene glycol (PEG) moiety to PTX still by a silicate linking group. Chapter II discussed the possibilities of utilizing silicates as cleaving points in polymer backbones for degradation purposes. For consistency, we defined the following nomenclature: polysilylethers (–CSi–OC– repeat units); polydisiloxanes (–CSi–O–SiC– repeat units); polysilaketals (–CO–Si–OC– repeat units); and polydialkoxy-/tri-/…-siloxanes (–CO–[Si–O]n–Si–OC– repeat units). We then synthesized a library of analogous small molecule compounds and studied their liabilities under different aqueous conditions. These provided essential information for polymer scientists to design polymers with Si–O bonds embedded in. Chapter III describes my work on proving a simple 1H NMR experiment to be a universal protocol to predict the polymerizability of a novel lactone in a ring-opening trans-esterification polymerization (ROTEP). We’ve done the experiments on 18 lactones and include all the data here as a reference. This simple experiment can surely help polymer chemists get a better understanding of the thermodynamic driving force of their new lactones before wasting a portion of the pristine sample. Finally, in Chapter IV I will talk about my contribution to the hexadehydro-Diels-Alder (HDDA) reaction that has been studied by the Hoye group for a decade. The HDDA reaction involves the cyclization between a diyne and a diynophile to form a benzyne intermediate, which will be trapped by trapping reagent in situ. This methodology is a very useful protocol to synthesize benzenoid scaffolds that are widely present in natural products. However, all HDDA precursor requires a 3-atom linker, or tether group between the diyne and the diynophile, to let the cyclization happen. This somehow limits the application of HDDA reaction. I particularly utilized the Lewis-pair interaction between pinacolate boron (BPin) and pyridine to form a virtual 3-atom linker between the diyne and diynophile. This is a breakthrough in the area where the access to the substrates is eased and we can synthesize a larger library of target molecules.