{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/115798"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/115798","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of a radical Ti(III)-mediated cyclization cascade to synthesize trans-decalones from epoxynitriles","abstract":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-11-11 without embargo terms","abstract_html":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-11-11 without embargo terms","abstract_has_math":false,"creators":["Milkovits, Amanda Anastasia"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Sarlah, David"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-05","date_published":"2022-05","updated_at":"2026-07-22T22:24:55Z","subjects":["synthesis","polyene cyclization","titanocene","titanium","epoxide ring-opening","trans-decalones","stereoselective","biomimetic"],"languages":["en","eng"],"rights":["Copyright 2022 Amanda Milkovits"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/115798","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Sarlah, David"]},{"key":"dc:creator","label":"Author","values":["Milkovits, Amanda Anastasia"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-05","2022-04-29"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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":["synthesis","polyene cyclization","titanocene","titanium","epoxide ring-opening","trans-decalones","stereoselective","biomimetic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2022 Amanda Milkovits"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/115798"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-11-11 without embargo terms","The student, Amanda Milkovits, accepted the attached license on 2022-04-29 at 10:43.","The student, Amanda Milkovits, submitted this Thesis for approval on 2022-04-29 at 10:48.","This Thesis was approved for publication on 2022-04-29 at 14:58.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17993 on 2022-11-11 at 17:54:07","Polyene cyclizations offer an elegant method to transform linear precursors into cyclic products. In particular, trans-decalins can be synthesized through two sequential ring formations. Starting from epoxynitrile olefins, Ti(III) can act as a radical initiator to open up the epoxide forming the tertiary free radical. This radical is then added into the alkene reversibly either kinetically via a 5-exo-trig ¬¬cyclization to give a cyclopentane ring with a secondary radical or thermodynamically via a 6-endo¬-trig cyclization to give the cyclohexane with the more stable tertiary radical. From the 6-membered intermediate, the radical adds into the nitrile to give the imine radical, which is hydrolyzed to the ketone. The goal was to take advantage of the stereochemistry of the epoxide precursors to provide a method for a stereospecific polyene cyclization to synthesize ¬trans-decalins with oxidation in either the equatorial or axial positions. Herein is described how this hypothesis was tested by using the cis and trans ¬isomers of trisubstituted epoxides to get to the axially and equatorially oxidized product respectively. Unfortunately, there was no stereospecificity; in all cases, the product was the equatorially oxidized trans¬-decalin. Disubstituted epoxides were also tested with the epoxide and protected or unprotected secondary alcohol syn to each other to give the equatorial product and with the epoxide and protected or unprotected secondary alcohol anti ¬to each other to give the axial product. Both substrates gave the thermodynamic trans¬-decalin with oxidation in the equatorial position. Overall, this radical cyclization method offers a facile synthesis of the thermodynamic trans-decalone with both the secondary alcohol and oxidized methyl group in the equatorial position. Selective protection of either the secondary or primary alcohol is possible depending on whether the disubstituted or trisubstituted epoxides are used."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Development of a radical Ti(III)-mediated cyclization cascade to synthesize trans-decalones from epoxynitriles"]}]}],"canonical_facts":{"dc:contributor":["Sarlah, David"],"dc:creator":["Milkovits, Amanda Anastasia"],"dc:date":["2022-05","2022-04-29"],"dc:description":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2022-11-11 without embargo terms","The student, Amanda Milkovits, accepted the attached license on 2022-04-29 at 10:43.","The student, Amanda Milkovits, submitted this Thesis for approval on 2022-04-29 at 10:48.","This Thesis was approved for publication on 2022-04-29 at 14:58.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17993 on 2022-11-11 at 17:54:07","Polyene cyclizations offer an elegant method to transform linear precursors into cyclic products. In particular, trans-decalins can be synthesized through two sequential ring formations. Starting from epoxynitrile olefins, Ti(III) can act as a radical initiator to open up the epoxide forming the tertiary free radical. This radical is then added into the alkene reversibly either kinetically via a 5-exo-trig ¬¬cyclization to give a cyclopentane ring with a secondary radical or thermodynamically via a 6-endo¬-trig cyclization to give the cyclohexane with the more stable tertiary radical. From the 6-membered intermediate, the radical adds into the nitrile to give the imine radical, which is hydrolyzed to the ketone. The goal was to take advantage of the stereochemistry of the epoxide precursors to provide a method for a stereospecific polyene cyclization to synthesize ¬trans-decalins with oxidation in either the equatorial or axial positions. Herein is described how this hypothesis was tested by using the cis and trans ¬isomers of trisubstituted epoxides to get to the axially and equatorially oxidized product respectively. Unfortunately, there was no stereospecificity; in all cases, the product was the equatorially oxidized trans¬-decalin. Disubstituted epoxides were also tested with the epoxide and protected or unprotected secondary alcohol syn to each other to give the equatorial product and with the epoxide and protected or unprotected secondary alcohol anti ¬to each other to give the axial product. Both substrates gave the thermodynamic trans¬-decalin with oxidation in the equatorial position. Overall, this radical cyclization method offers a facile synthesis of the thermodynamic trans-decalone with both the secondary alcohol and oxidized methyl group in the equatorial position. Selective protection of either the secondary or primary alcohol is possible depending on whether the disubstituted or trisubstituted epoxides are used."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/115798"],"dc:language":["en","eng"],"dc:rights":["Copyright 2022 Amanda Milkovits"],"dc:subject":["synthesis","polyene cyclization","titanocene","titanium","epoxide ring-opening","trans-decalones","stereoselective","biomimetic"],"dc:title":["Development of a radical Ti(III)-mediated cyclization cascade to synthesize trans-decalones from epoxynitriles"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:55Z"}