{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72256"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72256","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Development of Sequential Silylcarbocyclization Silicon-Based Cross-Coupling Reactions and Their Application in the Total Synthesis of Isodomoic Acid H","abstract":"A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. These alkylidenylsilanes underwent palladium-catalyzed cross-coupling with aryl iodides promoted by tetra-n-butylammonium fluoride, displaying a broad substrate scope. This catalytic system shows a broad compatibility towards substitution patterns, electronic properties, and heteroatoms. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and analogous heterocycles. This synthetic method was applied to the total synthesis of a marine natural product of the kanoid family, isodomoic acid H. This total synthesis was achieved via a short twelve step longest linear sequence, in which the key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne, a desilylative iodination reaction with an inversion of double bond configuration, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodide and the side-chain silanol. The mechanistic insight garnered during the investigation of the invertive desilylative iodination reaction enabled the accomplishment of a desilylative iodination reaction with an inversion of double bond configuration, thus opening up a promising synthetic route leading towards the total synthesis of isodomoic acid G, a congener of isodomoic acid H.","abstract_html":"A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. These alkylidenylsilanes underwent palladium-catalyzed cross-coupling with aryl iodides promoted by tetra-n-butylammonium fluoride, displaying a broad substrate scope. This catalytic system shows a broad compatibility towards substitution patterns, electronic properties, and heteroatoms. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and analogous heterocycles. This synthetic method was applied to the total synthesis of a marine natural product of the kanoid family, isodomoic acid H. This total synthesis was achieved via a short twelve step longest linear sequence, in which the key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne, a desilylative iodination reaction with an inversion of double bond configuration, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodide and the side-chain silanol. The mechanistic insight garnered during the investigation of the invertive desilylative iodination reaction enabled the accomplishment of a desilylative iodination reaction with an inversion of double bond configuration, thus opening up a promising synthetic route leading towards the total synthesis of isodomoic acid G, a congener of isodomoic acid H.","abstract_has_math":false,"creators":["Liu, Jack Hung-Chang"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Denmark, Scott E."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-17T21:28:53Z","date_published":"2014-12-17T21:28:53Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI3392195"],"render_values":[{"text":"(UMI)AAI3392195","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72256","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":["Liu, Jack Hung-Chang"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:28:53Z","10000-01-01","2009"]},{"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/2142/72256","(UMI)AAI3392195"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A sequential rhodium-catalyzed silylcarbocyclization of enynes parlayed with a palladium-catalyzed, silicon-based cross-coupling reaction has been developed. 1,6-Enynes reacted with benzyldimethylsilane in the presence of rhodium catalysts to afford five-membered rings bearing a (Z)-alkylidenylbenzylsilyl group. A variety of substitution patterns and heteroatom substituents were compatible. These alkylidenylsilanes underwent palladium-catalyzed cross-coupling with aryl iodides promoted by tetra-n-butylammonium fluoride, displaying a broad substrate scope. This catalytic system shows a broad compatibility towards substitution patterns, electronic properties, and heteroatoms. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and analogous heterocycles. This synthetic method was applied to the total synthesis of a marine natural product of the kanoid family, isodomoic acid H. This total synthesis was achieved via a short twelve step longest linear sequence, in which the key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne, a desilylative iodination reaction with an inversion of double bond configuration, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodide and the side-chain silanol. The mechanistic insight garnered during the investigation of the invertive desilylative iodination reaction enabled the accomplishment of a desilylative iodination reaction with an inversion of double bond configuration, thus opening up a promising synthetic route leading towards the total synthesis of isodomoic acid G, a congener of isodomoic acid H.","Made available in DSpace on 2014-12-17T21:28:53Z (GMT). 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A variety of substitution patterns and heteroatom substituents were compatible. These alkylidenylsilanes underwent palladium-catalyzed cross-coupling with aryl iodides promoted by tetra-n-butylammonium fluoride, displaying a broad substrate scope. This catalytic system shows a broad compatibility towards substitution patterns, electronic properties, and heteroatoms. All of the cross-coupling reactions proceeded in high yields under very mild conditions and with complete retention of double bond configuration, resulting in densely functionalized 3-(Z)-benzylidenecyclopentanes and analogous heterocycles. This synthetic method was applied to the total synthesis of a marine natural product of the kanoid family, isodomoic acid H. This total synthesis was achieved via a short twelve step longest linear sequence, in which the key transformations include a diastereoselective rhodium-catalyzed carbonylative silylcarbocyclization reaction of a vinylglycine-derived 1,6-enyne, a desilylative iodination reaction with an inversion of double bond configuration, as well as an alkenyl-alkenyl silicon-based cross-coupling reaction uniting the core alkenyl iodide and the side-chain silanol. The mechanistic insight garnered during the investigation of the invertive desilylative iodination reaction enabled the accomplishment of a desilylative iodination reaction with an inversion of double bond configuration, thus opening up a promising synthetic route leading towards the total synthesis of isodomoic acid G, a congener of isodomoic acid H.","Made available in DSpace on 2014-12-17T21:28:53Z (GMT). No. of bitstreams: 1 3392195.pdf: 4513508 bytes, checksum: 9468bfae2ec56e8cf2344f30825afa1b (MD5) Previous issue date: 2009","Embargo set by: Seth Robbins for item 72424 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","351 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009."],"dc:identifier":["http://hdl.handle.net/2142/72256","(UMI)AAI3392195"],"dc:subject":["Chemistry, Organic"],"dc:title":["The Development of Sequential Silylcarbocyclization Silicon-Based Cross-Coupling Reactions and Their Application in the Total Synthesis of Isodomoic Acid H"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:06Z"}