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Date of Award
Spring 2025
Document Type
Masters Thesis
Department or Program Affiliation
Chemistry
Degree Name
Master of Science (MS)
Department
Chemistry
First Advisor
O'Neil, Gregory (Gregory W.)
Second Advisor
Murphy, Amanda R.
Third Advisor
Vyvyan, James R.
Abstract
Silicon-oxygen heterocycles are synthetic intermediates that have been used for over 50 years. These compounds are particularly useful when combined with stereospecific desilylation reactions giving access to stereospecific 1,3-diols. To make these heterocycles, precious metal catalysts such as platinum, ruthenium, rhodium, or iridium are typically used. Here we have developed a one-pot reaction using tetrabutylammonium difluorotriphenylsilicate (TBAT) and diphenylsilane to give access to these systems without the use of precious metal catalysts. Subjecting β- or γ-hydroxy alkenes to these conditions gives oxasilolane and oxasilinane systems (5- and 6-memebered silicon oxygen heterocycles), while β-hydroxy epoxides afforded dioxasilinane systems (6-memebered heterocycles with a silicon and two oxygens). These systems are made with syn-selectivity (up to 5.2:1.0) with yields as high as 98% while being highly tolerant of substitutions. This reaction takes place via an anionic intermediate which requires resonance stabilization, but many different conjugated systems are tolerated. Tomao-Flemming oxidations of these systems allow for easy access to syn-1,3-diols. A two-step method was also developed for direct access to 1,3-diols from β-hydroxy epoxides. This reaction first forms a silyl ether using Grubbs 1st generation catalyst and diphenylsilane followed by activation by tetrabutylammonium fluoride (TBAF) or tetrabutylammonium difluorotriphenylsilicate (TBAT) affording 1,3-diols in moderate yields.
Type
Text
Keywords
Hydrosilylation, Oxasilinane, Oxasilolane, Dioxasilolane, TBAT, TBAF, Silicon, Silane, Reaction Development
Publisher
Western Washington University
OCLC Number
1523220687
Subject – LCSH
Hydrosilylation; Fluorine compounds; Organosilicon compounds; Heterocyclic compounds; Silane compounds; Epoxy compounds; Alkenes
Format
application/pdf
Genre/Form
masters theses
Language
English
Rights
Copying of this document in whole or in part is allowable only for scholarly purposes. It is understood, however, that any copying or publication of this document for commercial purposes, or for financial gain, shall not be allowed without the author’s written permission.
Rights Statement
http://rightsstatements.org/vocab/NKC/1.0/
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.
Recommended Citation
Jones, Adam P., "Fluoride-Promoted Hydroxyl-Directed Hydrosilylations of Epoxides and Alkenes" (2025). WWU Graduate School Collection. 1394.
https://cedar.wwu.edu/wwuet/1394