2026-09-20T17:49:37Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/430862022-01-13T07:54:21Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Rick L. Danheiser.
Austin, Wesley F
Massachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology. Department of Chemistry
2008-11-07T19:00:34Z
2008-11-07T19:00:34Z
2007
2008
http://hdl.handle.net/1721.1/43086
244391326
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, February 2008.
Vita.
Includes bibliographical references.
(Trialkylsilyl)vinylketenes ("TAS-vinylketenes") are versatile four-carbon building blocks in a variety of methods for the synthesis of carbocyclic and heterocyclic compounds. This thesis discusses the development of a new benzannulation strategy for the synthesis of phenols based on the reaction of TAS-vinylketenes with lithium ynolates. Studies have shown that the reaction proceeds by formation and electrocyclic ring closure of 3-oxidodienylketene intermediates, followed by an intramolecular 1,3-silyl migration to provide highly substituted 3-siloxy phenols. Further transformations of these products providing efficient access to ortho-benzoquinones and benzofuran, benzoxepine, and benzoxocine ring systems are described. Additionally, unsuccessful attempts to prepare TAS-vinylketenes by the rearrangement of siloxy alkynes and by cross-metathesis are discussed.
by Wesley F. Austin.
Ph.D.
244 [2] p.
eng
Massachusetts Institute of Technology
M.I.T. theses are protected by
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http://dspace.mit.edu/handle/1721.1/7582
Chemistry.
The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes
Thesis
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Publication
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<Abstract>(Trialkylsilyl)vinylketenes ("TAS-vinylketenes") are versatile four-carbon building blocks in a variety of methods for the synthesis of carbocyclic and heterocyclic compounds. This thesis discusses the development of a new benzannulation strategy for the synthesis of phenols based on the reaction of TAS-vinylketenes with lithium ynolates. Studies have shown that the reaction proceeds by formation and electrocyclic ring closure of 3-oxidodienylketene intermediates, followed by an intramolecular 1,3-silyl migration to provide highly substituted 3-siloxy phenols. Further transformations of these products providing efficient access to ortho-benzoquinones and benzofuran, benzoxepine, and benzoxocine ring systems are described. Additionally, unsuccessful attempts to prepare TAS-vinylketenes by the rearrangement of siloxy alkynes and by cross-metathesis are discussed.</Abstract>
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