The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes
Author(s)Austin, Wesley F
Massachusetts Institute of Technology. Dept. of Chemistry.
Rick L. Danheiser.
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(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.
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, February 2008.Vita.Includes bibliographical references.
DepartmentMassachusetts Institute of Technology. Dept. of Chemistry.
Massachusetts Institute of Technology