{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/54267"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/54267","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Vinylcyclopropanation of enones in [2+3] cyclopentene annulation: application to the total synthesis of (-)-retigeranic acid","abstract":"The addition of the Iithium dienolate 161a derived from ethyl 2-bromocrotonate (163) to several enones provided vinylcyclopropanes of type 165 which were converted by thermolysis to the corresponding cyclopentenes in an overall [2+3] annulation process. [see document for diagram of chemical compounds] The reactions of 161a with other electrophiles such as ketones, α,ß-unsaturated esters and α,ß-unsaturated aldehydes were also investigated. The possibility of asymmetric induction utilizing (-)-menthyl 2-bromocrotonate (169) was briefly investigated. An application of this methodology was expressed in the total synthesis of (-)- retigeranic acid (1), achieved in fifteen steps from menthene (187) in a convergent and enantioselective fashion. The key steps in this synthesis involved the vinylcyclopropanation of bicyclic enone 144 with the lithium dienolate of bromide 180, to provide vinylcyclopropanes 179 and, through their thermolytic rearrangement, the pentacyclic ketone 178, which was converted to the title compound. [see document for diagram of chemical compounds]","abstract_html":"The addition of the Iithium dienolate 161a derived from ethyl 2-bromocrotonate (163) to several enones provided vinylcyclopropanes of type 165 which were converted by thermolysis to the corresponding cyclopentenes in an overall [2+3] annulation process. [see document for diagram of chemical compounds] The reactions of 161a with other electrophiles such as ketones, α,ß-unsaturated esters and α,ß-unsaturated aldehydes were also investigated. The possibility of asymmetric induction utilizing (-)-menthyl 2-bromocrotonate (169) was briefly investigated. An application of this methodology was expressed in the total synthesis of (-)- retigeranic acid (1), achieved in fifteen steps from menthene (187) in a convergent and enantioselective fashion. The key steps in this synthesis involved the vinylcyclopropanation of bicyclic enone 144 with the lithium dienolate of bromide 180, to provide vinylcyclopropanes 179 and, through their thermolytic rearrangement, the pentacyclic ketone 178, which was converted to the title compound. [see document for diagram of chemical compounds]","abstract_has_math":false,"creators":["Radesca, Lilián A."],"institution":"Virginia Polytechnic Institute and State University","degree_name":"Ph. D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Hudlicky, Tomas"],"committee_members":["WoIfe, James F.","Mason, John G.","Kingston, David G. I.","White, Robert H."],"year":1989,"date_issued":"1989","date_published":"1989","updated_at":"2026-07-24T05:56:34Z","subjects":[],"languages":["en_US"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/54267","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Hudlicky, Tomas"]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["WoIfe, James F.","Mason, John G.","Kingston, David G. I.","White, Robert H."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Radesca, Lilián A."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2015-07-09T20:43:29Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2015-07-09T20:43:29Z"]},{"key":"dc:date.issued","label":"Date","values":["1989"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute and State University"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","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":["Ph. D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/54267"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The addition of the Iithium dienolate 161a derived from ethyl 2-bromocrotonate (163) to several enones provided vinylcyclopropanes of type 165 which were converted by thermolysis to the corresponding cyclopentenes in an overall [2+3] annulation process. [see document for diagram of chemical compounds] The reactions of 161a with other electrophiles such as ketones, α,ß-unsaturated esters and α,ß-unsaturated aldehydes were also investigated. The possibility of asymmetric induction utilizing (-)-menthyl 2-bromocrotonate (169) was briefly investigated. An application of this methodology was expressed in the total synthesis of (-)- retigeranic acid (1), achieved in fifteen steps from menthene (187) in a convergent and enantioselective fashion. The key steps in this synthesis involved the vinylcyclopropanation of bicyclic enone 144 with the lithium dienolate of bromide 180, to provide vinylcyclopropanes 179 and, through their thermolytic rearrangement, the pentacyclic ketone 178, which was converted to the title compound. [see document for diagram of chemical compounds]"]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Vinylcyclopropanation of enones in [2+3] cyclopentene annulation: application to the total synthesis of (-)-retigeranic acid"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Hudlicky, Tomas"],"dc:contributor.committeemember":["WoIfe, James F.","Mason, John G.","Kingston, David G. I.","White, Robert H."],"dc:contributor.department":["Chemistry"],"dc:creator":["Radesca, Lilián A."],"dc:date.accessioned":["2015-07-09T20:43:29Z"],"dc:date.available":["2015-07-09T20:43:29Z"],"dc:date.issued":["1989"],"dc:description.abstract":["The addition of the Iithium dienolate 161a derived from ethyl 2-bromocrotonate (163) to several enones provided vinylcyclopropanes of type 165 which were converted by thermolysis to the corresponding cyclopentenes in an overall [2+3] annulation process. [see document for diagram of chemical compounds] The reactions of 161a with other electrophiles such as ketones, α,ß-unsaturated esters and α,ß-unsaturated aldehydes were also investigated. The possibility of asymmetric induction utilizing (-)-menthyl 2-bromocrotonate (169) was briefly investigated. An application of this methodology was expressed in the total synthesis of (-)- retigeranic acid (1), achieved in fifteen steps from menthene (187) in a convergent and enantioselective fashion. The key steps in this synthesis involved the vinylcyclopropanation of bicyclic enone 144 with the lithium dienolate of bromide 180, to provide vinylcyclopropanes 179 and, through their thermolytic rearrangement, the pentacyclic ketone 178, which was converted to the title compound. [see document for diagram of chemical compounds]"],"dc:description.degree":["Ph. D."],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/54267"],"dc:language.iso":["en_US"],"dc:publisher":["Virginia Polytechnic Institute and State University"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["Vinylcyclopropanation of enones in [2+3] cyclopentene annulation: application to the total synthesis of (-)-retigeranic acid"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-24T05:56:34Z"}