{"id":{"repo_id":"colostate","oai_identifier":"oai:mountainscholar.org:10217/243837"},"canonical_url":"https://search.dev.ndltd.org/etd/colostate/oai:mountainscholar.org:10217/243837","repository":{"repo_id":"colostate","name":"Colorado State University","base_url":"https://api.mountainscholar.org/server/oai/request"},"display":{"title":"Development of a catalytic enantioselective intramolecular Stetter reaction: catalyst development and synthetic applications","abstract":"A triazolinylidene carbene-catalyzed enantioselective intramolecular Stetter reaction has been developed. The process involves direct conversion of an aldehyde into a chiral acyl anion equivalent and its addition into a pendant electron-deficient olefin. The development of chiral bicyclic nucleophilic carbene catalysts has allowed for increased efficiency and selectivity in this reaction, as well as an overall broadening of its synthetic utility. The highly stereoselective formation of five- and six-membered rings has been realized in this reaction manifold. Extensive catalyst development has identified a number of catalysts which often provide complementary reactivity and selectivity. Aliphatic and aromatic aldehydes both participate in the addition to a variety of Michael acceptors. Synthetically important enantioenriched 1,4-dicarbonyl compounds can be generated in a single operation from achiral materials. The Stetter reaction has been developed to construct challenging quaternary stereocenters with good efficiency and very high selectivity. The scope of this transformation is quite broad, and holds significant promise for further reaction development. Synthetic applications have been investigated in the arena of natural product synthesis. Progress has been made utilizing the Stetter reaction for a key bond construction in an effort to enantioselectively synthesize a complex alkaloid. The key Stetter reaction in this system affords the desired product in good yield and excellent enantioselectivity.","abstract_html":"A triazolinylidene carbene-catalyzed enantioselective intramolecular Stetter reaction has been developed. The process involves direct conversion of an aldehyde into a chiral acyl anion equivalent and its addition into a pendant electron-deficient olefin. The development of chiral bicyclic nucleophilic carbene catalysts has allowed for increased efficiency and selectivity in this reaction, as well as an overall broadening of its synthetic utility. The highly stereoselective formation of five- and six-membered rings has been realized in this reaction manifold. Extensive catalyst development has identified a number of catalysts which often provide complementary reactivity and selectivity. Aliphatic and aromatic aldehydes both participate in the addition to a variety of Michael acceptors. Synthetically important enantioenriched 1,4-dicarbonyl compounds can be generated in a single operation from achiral materials. The Stetter reaction has been developed to construct challenging quaternary stereocenters with good efficiency and very high selectivity. The scope of this transformation is quite broad, and holds significant promise for further reaction development. Synthetic applications have been investigated in the arena of natural product synthesis. Progress has been made utilizing the Stetter reaction for a key bond construction in an effort to enantioselectively synthesize a complex alkaloid. The key Stetter reaction in this system affords the desired product in good yield and excellent enantioselectivity.","abstract_has_math":false,"creators":["Kerr, Mark Steven, author","Rovis, Tomislav, advisor","Anderson, Oren P., committee member","Bernstein, Elliot R., committee member","McNeil, Michael, committee member","Williams, Robert M., committee member"],"institution":"Colorado State University. Libraries","degree_name":"Doctor of Philosophy (Ph.D.)","degree_level":"Doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007","date_published":"2007","updated_at":"2026-07-27T19:13:00Z","subjects":["organic chemistry"],"languages":["eng","English"],"rights":["Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://doi.org/10.25675/3.026524"],"render_values":[{"text":"https://doi.org/10.25675/3.026524","href":"https://doi.org/10.25675/3.026524","code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/10217/243837","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Kerr, Mark Steven, author","Rovis, Tomislav, advisor","Anderson, Oren P., committee member","Bernstein, Elliot R., committee member","McNeil, Michael, committee member","Williams, Robert M., committee member"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2026-03-26T18:32:21Z"]},{"key":"dc:date.issued","label":"Date","values":["2007"]},{"key":"dc:publisher","label":"Institution","values":["Colorado State University. Libraries"]},{"key":"dc:type","label":"Dc Type","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (Ph.D.)"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Colorado State University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["organic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10217/243837","https://doi.org/10.25675/3.026524"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A triazolinylidene carbene-catalyzed enantioselective intramolecular Stetter reaction has been developed. The process involves direct conversion of an aldehyde into a chiral acyl anion equivalent and its addition into a pendant electron-deficient olefin. The development of chiral bicyclic nucleophilic carbene catalysts has allowed for increased efficiency and selectivity in this reaction, as well as an overall broadening of its synthetic utility. The highly stereoselective formation of five- and six-membered rings has been realized in this reaction manifold. Extensive catalyst development has identified a number of catalysts which often provide complementary reactivity and selectivity. Aliphatic and aromatic aldehydes both participate in the addition to a variety of Michael acceptors. Synthetically important enantioenriched 1,4-dicarbonyl compounds can be generated in a single operation from achiral materials. The Stetter reaction has been developed to construct challenging quaternary stereocenters with good efficiency and very high selectivity. The scope of this transformation is quite broad, and holds significant promise for further reaction development. Synthetic applications have been investigated in the arena of natural product synthesis. Progress has been made utilizing the Stetter reaction for a key bond construction in an effort to enantioselectively synthesize a complex alkaloid. The key Stetter reaction in this system affords the desired product in good yield and excellent enantioselectivity."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["doctoral dissertations"]},{"key":"dc:title","label":"Title","values":["Development of a catalytic enantioselective intramolecular Stetter reaction: catalyst development and synthetic applications"]}]}],"canonical_facts":{"dc:creator":["Kerr, Mark Steven, author","Rovis, Tomislav, advisor","Anderson, Oren P., committee member","Bernstein, Elliot R., committee member","McNeil, Michael, committee member","Williams, Robert M., committee member"],"dc:date.accessioned":["2026-03-26T18:32:21Z"],"dc:date.issued":["2007"],"dc:description.abstract":["A triazolinylidene carbene-catalyzed enantioselective intramolecular Stetter reaction has been developed. The process involves direct conversion of an aldehyde into a chiral acyl anion equivalent and its addition into a pendant electron-deficient olefin. The development of chiral bicyclic nucleophilic carbene catalysts has allowed for increased efficiency and selectivity in this reaction, as well as an overall broadening of its synthetic utility. The highly stereoselective formation of five- and six-membered rings has been realized in this reaction manifold. Extensive catalyst development has identified a number of catalysts which often provide complementary reactivity and selectivity. Aliphatic and aromatic aldehydes both participate in the addition to a variety of Michael acceptors. Synthetically important enantioenriched 1,4-dicarbonyl compounds can be generated in a single operation from achiral materials. The Stetter reaction has been developed to construct challenging quaternary stereocenters with good efficiency and very high selectivity. The scope of this transformation is quite broad, and holds significant promise for further reaction development. Synthetic applications have been investigated in the arena of natural product synthesis. Progress has been made utilizing the Stetter reaction for a key bond construction in an effort to enantioselectively synthesize a complex alkaloid. The key Stetter reaction in this system affords the desired product in good yield and excellent enantioselectivity."],"dc:format.medium":["doctoral dissertations"],"dc:identifier.uri":["https://hdl.handle.net/10217/243837","https://doi.org/10.25675/3.026524"],"dc:language":["English"],"dc:language.iso":["eng"],"dc:publisher":["Colorado State University. Libraries"],"dc:rights":["Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright."],"dc:subject":["organic chemistry"],"dc:title":["Development of a catalytic enantioselective intramolecular Stetter reaction: catalyst development and synthetic applications"],"dc:type":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Doctor of Philosophy (Ph.D.)"],"thesis:institution_name":["Colorado State University"]},"updated_at":"2026-07-27T19:13:00Z"}