{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70305"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70305","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"On the Stereochemistry of Allylmetal-Aldehyde Condensations (Allyltrimethylsilane, Allyltributylstannane, Homoallylic Alcohols)","abstract":"The stereochemical course of the intramolecular allylmetal-aldehyde condensation of allylsilane 3a, allylstannane 3b, and pentadienylsilane 6 has been investigated. A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.","abstract_html":"The stereochemical course of the intramolecular allylmetal-aldehyde condensation of allylsilane 3a, allylstannane 3b, and pentadienylsilane 6 has been investigated. A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.","abstract_has_math":false,"creators":["Weber, Eric John"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:31Z","date_published":"2014-12-15T23:18:31Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8521900"],"render_values":[{"text":"(UMI)AAI8521900","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70305","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Weber, Eric John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:31Z","10000-01-01","1985"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70305","(UMI)AAI8521900"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The stereochemical course of the intramolecular allylmetal-aldehyde condensation of allylsilane 3a, allylstannane 3b, and pentadienylsilane 6 has been investigated. A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.","Made available in DSpace on 2014-12-15T23:18:31Z (GMT). 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A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.","Made available in DSpace on 2014-12-15T23:18:31Z (GMT). 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