The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes
Name
244391326-MIT.pdf
Description
Full printable version
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10.25 MB
Format
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Checksum (MD5)
fc3e711a4d7c58060bbd117ffa4f508b
Author(s)
Austin, Wesley F
Advisor(s)
Rick L. Danheiser.
Date Issued
2008
Publisher
Massachusetts Institute of Technology
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.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, February 2008.
Vita.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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