The Claisen rearrangement of 4-allyloxyisoquinolines, and, The Bradsher cycloaddition of 4-alkoxyisoquinolinium salts: Synthesis of a model of the BC ring system of the angucylines.
Item
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Title
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The Claisen rearrangement of 4-allyloxyisoquinolines, and, The Bradsher cycloaddition of 4-alkoxyisoquinolinium salts: Synthesis of a model of the BC ring system of the angucylines.
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Identifier
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AAI9417497
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identifier
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9417497
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Creator
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Nicolas, Tony Eddy.
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Contributor
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Adviser: Richard W. Franck
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Date
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1994
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Organic | Chemistry, Pharmaceutical
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Abstract
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A general method for the functionalization of 4-hydroxyisoquinoline has been developed. This general procedure has been applied to the synthesis of 4-allyloxyisoquinolines possessing various substituents at C2 of the allylic moiety. These isoquinolinyl ethers have been found to readily undergo the Claisen rearrangement to provide 3-alkyl-4-hydroxyisoquinolines. The two-step sequence constitutes a convenient way of introducing alkyl substituents at C3. Attempts were made to further elaborate the Claisen products to enol ether 27, a structure which embodies all the requisite functionalities for an intramolecular Bradsher cycloaddition. In a parallel study of the intermolecular Bradsher cycloaddition of 4-alkoxyisoquinolinium salts, the reaction was elaborated into a powerful methodology for the introduction of the cis-hydroxyls of the angucyclines 9a-12b ring junction with the concomitant placement of the C1 carbonyl. These studies have culminated in a convenient synthesis of the BC ring 355 of the angucyclines.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
