{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/24450"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/24450","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Palladium catalyzed cross-coupling reactions of allyl- and vinylsilanes","abstract":"Palladium-catalyzed cross-coupling of γ-substituted allylic silanolates with aryl bromides was investigated. It was discovered that γ-selectivity is heavily influenced by the substituents at silicon. It is proposed that undergoing an activated pathway significantly lowers the selectivity of the reaction. A major side-product of this reaction was discovered and conditions were developed to suppress the undesired reaction. It is proposed that the side reaction shares at least two intermediates with the desired cross-coupling reaction. The use of arsenic ligands and elevated temperatures mildly suppressed the side-reaction and further studies are needed to completely prevent the unwanted pathway from occurring. The development and application of a 1,2-differentiated bissilylethene moiety has been studied. Moderate yields are obtained in the fluoride-free coupling with aryl iodides under mild conditions. When the cross-coupling reaction is conducted with aryl bromides poor yields of the desired product are obtained. The reactive silanolate species was discovered to dimerize to a non-competent disiloxane species at elevated temperatures. Hemilabile phosphine ligands and basic additives can be employed to facilitate the cross-coupling with aryl bromides; however, further studies are needed to prevent dimerization of the silanolate from occurring.","abstract_html":"Palladium-catalyzed cross-coupling of γ-substituted allylic silanolates with aryl bromides was investigated. It was discovered that γ-selectivity is heavily influenced by the substituents at silicon. It is proposed that undergoing an activated pathway significantly lowers the selectivity of the reaction. A major side-product of this reaction was discovered and conditions were developed to suppress the undesired reaction. It is proposed that the side reaction shares at least two intermediates with the desired cross-coupling reaction. The use of arsenic ligands and elevated temperatures mildly suppressed the side-reaction and further studies are needed to completely prevent the unwanted pathway from occurring. The development and application of a 1,2-differentiated bissilylethene moiety has been studied. Moderate yields are obtained in the fluoride-free coupling with aryl iodides under mild conditions. When the cross-coupling reaction is conducted with aryl bromides poor yields of the desired product are obtained. The reactive silanolate species was discovered to dimerize to a non-competent disiloxane species at elevated temperatures. Hemilabile phosphine ligands and basic additives can be employed to facilitate the cross-coupling with aryl bromides; however, further studies are needed to prevent dimerization of the silanolate from occurring.","abstract_has_math":false,"creators":["Bailey, Aaron D."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Denmark, Scott E."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-25T14:24:58Z","date_published":"2011-05-25T14:24:58Z","updated_at":"2026-07-22T22:25:23Z","subjects":["Palladium-catalyzed cross-coupling reactions","allylic silanes","vinylsilanes"],"languages":["en"],"rights":["Copyright 2011 Aaron D. Bailey"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/24450","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E."]},{"key":"dc:creator","label":"Author","values":["Bailey, Aaron D."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-25T14:24:58Z","2013-05-26T10:00:16Z","2011-05"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"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":["Palladium-catalyzed cross-coupling reactions","allylic silanes","vinylsilanes"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2011 Aaron D. 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The development and application of a 1,2-differentiated bissilylethene moiety has been studied. Moderate yields are obtained in the fluoride-free coupling with aryl iodides under mild conditions. When the cross-coupling reaction is conducted with aryl bromides poor yields of the desired product are obtained. The reactive silanolate species was discovered to dimerize to a non-competent disiloxane species at elevated temperatures. Hemilabile phosphine ligands and basic additives can be employed to facilitate the cross-coupling with aryl bromides; however, further studies are needed to prevent dimerization of the silanolate from occurring.","Item withdrawn by Rebecca Bryant (rabryant@illinois.edu) on 2010-12-21T21:59:57Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 2 Bailey_Aaron.doc: 2535424 bytes, checksum: 8c93c30661b01a7317e70a46a749daeb (MD5) Bailey_Aaron.pdf: 3201845 bytes, checksum: 502f625e744fefc3433225cdd20bbd46 (MD5)","Made available in DSpace on 2011-05-25T14:24:58Z (GMT). No. of bitstreams: 2 Bailey_Aaron.pdf: 3202703 bytes, checksum: 478651e68f2e29a609b48545f6cde46b (MD5) license.txt: 4062 bytes, checksum: 5ab59c126f17ca37ac2cd27f7137b2d2 (MD5)","Item marked as restricted to the 'Administrator' Group (id=1) by William Ingram (wingram2@illinois.edu) on 2011-05-25T14:29:41Z Item is restricted until 2013-05-25T14:29:35Z","Item reinstated by Sarah Shreeves (sshreeve@illinois.edu) on 2013-05-26T10:00:16Z Item was in collections: University of Illinois Dissertations and Theses (ID: 204) Dissertations and Theses - Chemistry (ID: 676) No. of bitstreams: 3 Bailey_Aaron.pdf.txt: 239468 bytes, checksum: f622c4dc0949bff017802189c3bdb1fe (MD5) Bailey_Aaron.pdf: 3202703 bytes, checksum: 478651e68f2e29a609b48545f6cde46b (MD5) license.txt: 4062 bytes, checksum: 5ab59c126f17ca37ac2cd27f7137b2d2 (MD5)","Item released from any restrictions by Sarah Shreeves (sshreeve@illinois.edu) on 2013-05-26T10:00:16Z"]},{"key":"dc:title","label":"Title","values":["Palladium catalyzed cross-coupling reactions of allyl- and vinylsilanes"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Bailey, Aaron D."],"dc:date":["2011-05-25T14:24:58Z","2013-05-26T10:00:16Z","2011-05"],"dc:description":["Palladium-catalyzed cross-coupling of γ-substituted allylic silanolates with aryl bromides was investigated. It was discovered that γ-selectivity is heavily influenced by the substituents at silicon. It is proposed that undergoing an activated pathway significantly lowers the selectivity of the reaction. A major side-product of this reaction was discovered and conditions were developed to suppress the undesired reaction. It is proposed that the side reaction shares at least two intermediates with the desired cross-coupling reaction. The use of arsenic ligands and elevated temperatures mildly suppressed the side-reaction and further studies are needed to completely prevent the unwanted pathway from occurring. The development and application of a 1,2-differentiated bissilylethene moiety has been studied. Moderate yields are obtained in the fluoride-free coupling with aryl iodides under mild conditions. When the cross-coupling reaction is conducted with aryl bromides poor yields of the desired product are obtained. The reactive silanolate species was discovered to dimerize to a non-competent disiloxane species at elevated temperatures. Hemilabile phosphine ligands and basic additives can be employed to facilitate the cross-coupling with aryl bromides; however, further studies are needed to prevent dimerization of the silanolate from occurring.","Item withdrawn by Rebecca Bryant (rabryant@illinois.edu) on 2010-12-21T21:59:57Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 2 Bailey_Aaron.doc: 2535424 bytes, checksum: 8c93c30661b01a7317e70a46a749daeb (MD5) Bailey_Aaron.pdf: 3201845 bytes, checksum: 502f625e744fefc3433225cdd20bbd46 (MD5)","Made available in DSpace on 2011-05-25T14:24:58Z (GMT). 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Bailey"],"dc:subject":["Palladium-catalyzed cross-coupling reactions","allylic silanes","vinylsilanes"],"dc:title":["Palladium catalyzed cross-coupling reactions of allyl- and vinylsilanes"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:23Z"}