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[4 + 1] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones

Author(s)
Davie, Christopher P
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[Four plus one] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones
Other Contributors
Massachusetts Institute of Technology. Dept. of Chemistry.
Advisor
Rick L. Danheiser.
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M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582
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Abstract
(Trialkylsilyl)vinylketenes ("(TAS)vinylketenes") and (trialkylsilyl)arylketenes ("(TAS)- arylketenes") function as versatile four-carbon building blocks for the synthesis of carbocyclic and heterocyclic compounds. A new [4 + 1] annulation strategy for the synthesis of substituted 2-indanones, based on the reaction of TAS-arylketenes with trimethylsilyl diazomethane, has been developed. In addition, a new class of carbenoid reagents for our previously reported [4 + 1] cyclopentenone annulation has been identified. Studies have shown that the reaction of a- benzotriazolyl organolithium compounds (prepared via metallation of readily available N- substituted benzotriazole derivatives) with (TAS)vinylketenes generates dienolate intermediates which cyclize to form cyclopentenones. Most cases of the annulation proceed with a high level of diastereoselectivity, and deliver highly substituted and functionalized 2-silylcyclopentenones in good yield. Furthermore, the vinylsilane moiety incorporated in the [4 + 1] annulation products provides a useful handle for further synthetic transformations. Preliminary studies focused on elaboration of the cyclopentenone products have laid the groundwork for future applications of this [4 + 1] annulation methodology.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005.
 
Vita.
 
Includes bibliographical references.
 
Date issued
2005
URI
http://hdl.handle.net/1721.1/33648
Department
Massachusetts Institute of Technology. Department of Chemistry
Publisher
Massachusetts Institute of Technology
Keywords
Chemistry.

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