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Date of Award
Department or Program Affiliation
Chemistry Department of WWU
Master of Science (MS)
O'Neil, Gregory (Gregory W.)
Vyvyan, James R.
Larsen, Michael B.
With the recent discovery of an iodine mediated rearrangement of diallylsilanes, we set out to investigate a similar fluorine mediated rearrangement, aimed at introducing a new method for synthesizing organofluorine compounds. Interest in incorporating fluorine into organic molecules has grown significantly in recent years, primarily for medicinal applications. Since certain fluorination methods require the use of mCPBA, a common epoxidizing reagent, control experiments were performed on the reaction of several diallylsilanes with mCPBA, anticipating that a competing epoxidation of the diallylsilanes might occur. It was found that the formation of the hydroxy ester occurred through a regioselective epoxide opening from the carboxylic acid derivative of mCPBA. This was later mitigated by the addition of a basic buffer to yield the epoxysilanes. Various Lewis and Bronsted acids were screened to promote an intramolecular epoxide opening, however it was observed that Triethylamine trihydrofluoride (HF TEA) had complete regioselective fluoride ring opening of the given epoxide under mild conditions. To our knowledge this type of fluorine ring opening has not been described. Attachment of different ligands on silicon permits the tunability and activation of the so-called beta silyl effect. A range of epoxysilanes containing different groups on silicon were studied to investigate the rate, stereoselectivity, and further functionalization.
Organic Chemistry, Fluorine, Silicon, Fluorohydrin, Fluorosilicon gauche effect
Western Washington University
Subject – LCSH
Fluorination; Fluorine; Nucleophilic reactions; Chemistry, Organic
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Clover, Alexie W., "New Synthetic Methods Based on Silicon-Tethered Nucleophilic Addition Reactions" (2023). WWU Graduate School Collection. 1202.
Available for download on Thursday, November 30, 2023