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Reactivity of substituted 4-Pyridones in normal and inverse demand Diels-Alder cycloaddition

UNCW Author/Contributor (non-UNCW co-authors, if there are any, appear on document)
Christopher J. MacNevin (Creator)
Institution
The University of North Carolina Wilmington (UNCW )
Web Site: http://library.uncw.edu/

Abstract: The synthesis of the decahydroquinoline ring system has been explored extensively due to its appearance within many biologically active natural alkaloids. New compounds containing such a moiety are being discovered on an ongoing basis. The present work has sought to develop an alternative synthetic pathway to this system through the use of Diels-Alder [4 + 2] cycloaddition chemistry. The initial focus of this research was on the development of an activated dienophile derived from 4-pyridone. Two such compounds were eventually synthesized, N-tosyl-3- formyl-5,6-dihydropyridin-4-one, and N-t-butoxycarbonyl-3-formyl-5,6-dihydropyridin- 4-one. The reactivity of these compounds with several different dienes was then investigated in an effort to obtain the desired decahydroquinoline cycloadduct. Under inverse electron demand Diels-Alder conditions, the synthesized compounds reacted with ethyl vinyl ether to consistently produce pyran containing bicyclic adducts under mild conditions. The products contained a mixture of isomers in varying ratio relative to the nitrogen substituent present. Non-activated dienes did not react with the dienophiles under normal demand conditions even with the addition of lewis acid catalysts. However, cycloadducts were formed through reaction with the highly activated diene 1-dimethylamino-3-tertbutyldimethylsiloxy- 1,3-butadiene. The products did not resemble the target decahydroquinoline system but instead appeared to be the result of reaction with the formyl group substituent, acting as a heterodienophile, to yield a dihydropyranone ring bridged to C-3 of the original pyridone derived dienophile.

Additional Information

Publication
Thesis
A Thesis Submitted to the University of North Carolina Wilmington in Partial Fulfillment of the Requirements for the Degree of Master of Science
Language: English
Date: 2009
Keywords
Chemical reactions, Diels-Alder reaction, Diolefins, Ring formation (Chemistry)
Subjects
Diels-Alder reaction
Ring formation (Chemistry)
Diolefins
Chemical reactions