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Date of Award
Restricted Thesis: Campus only access
Bachelor of Science
Dr. Chiles Wade Downey
In the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf), halides and other charged nucleophiles readily open epoxides under ambient conditions. When a moderate base is also present, epoxides like styrene oxide can rearrange into aldehydes for subsequent aldol reactions with enol silanes.
Cyclohexene oxide undergoes opening by triflate, iodide, or bromide in the presence of TMSOTf. Silylated styrene oxide and 2-( 4-bromophenyl)oxirane can also undergo this chemistry, resulting in a variety of halo alcohols. Formation of the least substituted alcohol is favored at low temperatures (namely -78 °C). When 1-( 4- chlorophyl) oxirane was exposed to TMSOTf and iodide, the aryl halo alcohol was generated as expected but so was a second, more interesting product: a styrene derivative. We propose that the styrene forms as a result of deoxygenating the iodide product via TMSI (a byproduct generated under the reaction conditions). Low temperatures and short reaction times favor the iodide product whereas higher temperatures and longer reaction times drive the reaction to the styrene derivative.
Yeutter, Nicholas Clayton, "Silyl triflate-mediated openings of epoxides" (2015). Honors Theses. 870.