Microwave-Assisted Thermolysis of ortho-Substituted Aroylsilanes
Marc Tremblay
Master of Science
Department of Chemistry
University of Toronto
2008
The microwave-assisted thermolysis of ortho-substituted aroylsilanes has been investigated. When irradiated at 250ºC in DMSO or o‑dichlorobenzene for 10 minutes, aroylsilanes form siloxycarbenes that react following different pathways depending on the solvent and the structure of the starting material. It is shown that in the case of substrates having an O‑allyl or an O‑propargyl chain ortho to the acylsilane, cycloaddition occurs followed by a cascade ring opening to give respectively chroman‑4-one and chromen‑4-one derivatives in up to 66% yield. Among the major competitive pathways were the insertion of the siloxycarbene into allylic C–H bonds and decomposition of the acylsilane group to the corresponding aldehyde, followed by Claisen rearrangement.
| Identifer | oai:union.ndltd.org:TORONTO/oai:tspace.library.utoronto.ca:1807/11168 |
| Date | 30 July 2008 |
| Creators | Tremblay, Marc |
| Contributors | Dong, Vy Maria |
| Source Sets | University of Toronto |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
| Format | 1861138 bytes, application/pdf |
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