{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/43086"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/43086","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes","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_html":"(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_has_math":false,"creators":["Austin, Wesley F"],"institution":"Massachusetts Institute of Technology","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Dept. of Chemistry.","school":null,"contributors":[],"advisors":["Rick L. Danheiser."],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008","date_published":"2008","updated_at":"2026-07-22T22:21:59Z","subjects":["Chemistry."],"languages":["eng"],"rights":["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."],"rights_urls":["http://dspace.mit.edu/handle/1721.1/7582"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1721.1/43086","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Rick L. Danheiser."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Austin, Wesley F"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2008-11-07T19:00:34Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2008-11-07T19:00:34Z"]},{"key":"dc:date.issued","label":"Date","values":["2008"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["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."]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://dspace.mit.edu/handle/1721.1/7582"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1721.1/43086"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, February 2008.","Vita.","Includes bibliographical references."]},{"key":"dc:description.abstract","label":"Abstract","values":["(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."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Rick L. Danheiser."],"dc:contributor.department":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:creator":["Austin, Wesley F"],"dc:date.accessioned":["2008-11-07T19:00:34Z"],"dc:date.available":["2008-11-07T19:00:34Z"],"dc:date.issued":["2008"],"dc:description":["Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, February 2008.","Vita.","Includes bibliographical references."],"dc:description.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."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["http://hdl.handle.net/1721.1/43086"],"dc:language.iso":["eng"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["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."],"dc:rights.uri":["http://dspace.mit.edu/handle/1721.1/7582"],"dc:subject":["Chemistry."],"dc:title":["The synthesis and benzannulation reactions of (trialkylsilyl)vinylketenes"],"dc:type":["Thesis"]},"updated_at":"2026-07-22T22:21:59Z"}