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Dissertation
Mechanistic studies of the sigmatropic rearrangement of o-allyl nitronic esters to y,o-unsaturated nitro naphthalene derivatives and nitro substituted cyclohexene derivatives
Doctor of Philosophy (Ph.D.), Drexel University
Sep 2010
DOI:
https://doi.org/10.17918/etd-3385
Abstract
The Claisen rearrangement of allyl vinyl ethers is a widely used synthetic reaction. It was found that a-allyl nitronic esters, readily obtained from tin(IV)-catalyzed Diels-Alder reactions using ~-nitrostyrene as the diene component undergo thermal (20-90°C) [3,3]-sigmatropic rearrangement to y,o-unsaturated nitro compounds in a process very similar to the Claisen rearrangement. The a-allyl nitronic ester rearrangement provides stereocontrolled access to diastereomeric 1 ,2,3,4,4a,5,6, 7-octahydro-5-nitronaphthalene derivatives and 3-nitro cyclohexene derivatives. Thermal isomerization of nitro compounds from cis- to trans-2-nitro-3-phenyl isomers was observed at higher temperature (lOO-150°C). The y,o-unsaturated nitro compounds are also readily obtained through traditional Diels-Alder reactions in which ~-nitrostyrene functions as the dienophile. However, in the traditional Diels-Alder reactions the y,o-unsaturated nitro compounds are obtained as an inseparable mixture of diastereomers and regioisomers in the traditional Diels-Alder reactions. The difficulty in separating diastereoisomers of y,ounsaturated nitro compounds is avoided by selectively rearranging nitronic esters to the corresponding nitro compounds. This is a newly discovered rearrangement process of nitronic esters, and it has been successfully applied to two systems. Diels-Alder cycloaddition followed by rearrangement is synthetically useful in preparation of purey,o-unsaturated nitro compounds.
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Details
- Title
- Mechanistic studies of the sigmatropic rearrangement of o-allyl nitronic esters to y,o-unsaturated nitro naphthalene derivatives and nitro substituted cyclohexene derivatives
- Creators
- Alma Pipic - DU
- Contributors
- Peter A. Wade (Advisor) - Drexel University (1970-)
- Awarding Institution
- Drexel University
- Degree Awarded
- Doctor of Philosophy (Ph.D.)
- Publisher
- Drexel University; Philadelphia, Pennsylvania
- Resource Type
- Dissertation
- Language
- English
- Academic Unit
- College of Arts and Sciences; Chemistry; Drexel University
- Other Identifier
- 3385; 991014632161804721