2026-09-20T10:43:19Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/336482022-01-13T07:54:21Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Rick L. Danheiser.
Davie, Christopher P
Massachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2006-07-31T15:20:04Z
2006-07-31T15:20:04Z
2005
2005
http://hdl.handle.net/1721.1/33648
64395349
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005.
Vita.
Includes bibliographical references.
(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.
by Christopher P. Davie.
Ph.D.
187 leaves
7836758 bytes
7844601 bytes
application/pdf
application/pdf
eng
Massachusetts Institute of Technology
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
Chemistry.
[4 + 1] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones
[Four plus one] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones
Thesis
application/pdf
Publication
unknown
unknown
<Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="85890788-1a2a-4e70-bf39-ac30fe8370c4">
<Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type>
<Language>eng</Language>
<Title>[4 + 1] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones</Title>
<Subtitle>[Four plus one] annulation reactions of (trialkylsilyl)ketenes : synthesis of substituted indanones and cyclopentenones</Subtitle>
<PublishedIn>
<Publication>
</Publication>
</PublishedIn>
<PublicationDate>2005</PublicationDate>
<Authors>
<Author>
<DisplayName>Davie, Christopher P</DisplayName>
<Affiliation>
<OrgUnit>
</OrgUnit>
</Affiliation>
</Author>
</Authors>
<Editors>
</Editors>
<Publishers>
<Publisher>
<DisplayName>Massachusetts Institute of Technology</DisplayName>
<OrgUnit />
</Publisher>
</Publishers>
<License>http://dspace.mit.edu/handle/1721.1/7582</License>
<Keyword>Chemistry.</Keyword>
<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.</Abstract>
<Access xmlns="http://purl.org/coar/access_right"
>
</Access>
</Publication>