An unprecedented anionic condensation, fragmentation, and elimination sequence from the coupling of bicyclo[2.2.1]heptenones with aldehydes is described. This reaction leads to the stereoselective formation of disubstituted five-membered rings which are present in a wide array of bioactive molecules. Oxabicyclo[2.2.1]heptenone 106 also undergoes two-carbon ring expansions when subjected to anionic conditions and Michael acceptors. As an outgrowth of this interesting chemistry, we have been able to access the carbon skeleton of oxygenated cembranoids by subjecting bis-activated ene-yne to the enolate from oxabicyclo[2.2.1]heptenone 106. In order to demonstrate the synthetic utility of the anionic condensation, fragmentation, and elimination reaction, we have applied it to the synthesis of nortetillapyrone.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/279938 |
| Date | January 2002 |
| Creators | Xu, Qing |
| Contributors | Rainier, Jon D. |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | en_US |
| Detected Language | English |
| Type | text, Dissertation-Reproduction (electronic) |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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