{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/19549"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/19549","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Dioxirane-mediated epoxidation of alkenes: The development of catalytic and asymmetric protocols","abstract":"A practical, general and efficient protocol for the catalytic epoxidation of alkenes has been developed. The in situ generation of reactive dioxiranes capable of epoxidizing a variety of alkenes under biphasic conditions has been accomplished using phase transfer catalysts bearing a carbonyl group. Optimal epoxidation conditions employ 10 mol % of 1-dodecyl-1-methyl-4-oxopiperidinium trifluoromethanesulfonate (9d$\\sp+$OTf$\\sp-)$ in a $\\rm CH\\sb2Cl\\sb2$/pH $7.5{-}8.0$ biphase using potassium monoperoxosulfate (Oxone) as the oxidant. Optimization of the conditions identified (1) slow addition rate, (2) pH 7.5-8.0, (3) n-dodecyl chain, and (4) the triflate salt as key experimental and structural variables.","abstract_html":"A practical, general and efficient protocol for the catalytic epoxidation of alkenes has been developed. The in situ generation of reactive dioxiranes capable of epoxidizing a variety of alkenes under biphasic conditions has been accomplished using phase transfer catalysts bearing a carbonyl group. Optimal epoxidation conditions employ 10 mol % of 1-dodecyl-1-methyl-4-oxopiperidinium trifluoromethanesulfonate (9d$\\sp+$OTf$\\sp-)$ in a $\\rm CH\\sb2Cl\\sb2$/pH $7.5{-}8.0$ biphase using potassium monoperoxosulfate (Oxone) as the oxidant. Optimization of the conditions identified (1) slow addition rate, (2) pH 7.5-8.0, (3) n-dodecyl chain, and (4) the triflate salt as key experimental and structural variables.","abstract_has_math":true,"creators":["Forbes, David Christopher"],"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":2011,"date_issued":"2011-05-07T12:11:06Z","date_published":"2011-05-07T12:11:06Z","updated_at":"2026-07-22T22:25:14Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1996 Forbes, David Christopher"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591087567","AAI9702514","(UMI)AAI9702514"],"render_values":[{"text":"9780591087567","href":null,"code":true},{"text":"AAI9702514","href":null,"code":true},{"text":"(UMI)AAI9702514","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/19549","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":["Forbes, David Christopher"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:11:06Z","10000-01-01","1996"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1996 Forbes, David Christopher"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591087567","AAI9702514","(UMI)AAI9702514","http://hdl.handle.net/2142/19549"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A practical, general and efficient protocol for the catalytic epoxidation of alkenes has been developed. The in situ generation of reactive dioxiranes capable of epoxidizing a variety of alkenes under biphasic conditions has been accomplished using phase transfer catalysts bearing a carbonyl group. Optimal epoxidation conditions employ 10 mol % of 1-dodecyl-1-methyl-4-oxopiperidinium trifluoromethanesulfonate (9d$\\sp+$OTf$\\sp-)$ in a $\\rm CH\\sb2Cl\\sb2$/pH $7.5{-}8.0$ biphase using potassium monoperoxosulfate (Oxone) as the oxidant. Optimization of the conditions identified (1) slow addition rate, (2) pH 7.5-8.0, (3) n-dodecyl chain, and (4) the triflate salt as key experimental and structural variables.","Efforts to develop an asymmetric epoxidation of alkene protocol using chiral, non-racemic ketone promoters are also reported. Chlorodifluoroketone promoter 36 was synthesized in 13 steps and subjected to our standard epoxidation of alkenes system and resulted in complete conversion when the reaction solution was emulsified and a level of asymmetric induction of 14% ee.","Also described is a stereochemical study on the intramolecular hydrosilylation of $\\alpha,\\beta$-unsaturated esters. The intramolecular hydrosilylation of several 3-methyl-4-siloxy-2-butenoates afforded cis-disubstituted $\\gamma$-lactones after desilylation. The diastereoinduction was sensitive to the bulk of the allylic substituents, but not to the groups on silicon. The origin of asymmetric induction is believed to be the A$\\sp{1,2}$ strain from the $\\beta$-methyl group.","Made available in DSpace on 2011-05-07T12:11:06Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702514.pdf: 10992081 bytes, checksum: f33508f4ec3da65394ec3773cb111d61 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:37:47Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:15:36-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Dioxirane-mediated epoxidation of alkenes: The development of catalytic and asymmetric protocols"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E."],"dc:creator":["Forbes, David Christopher"],"dc:date":["2011-05-07T12:11:06Z","10000-01-01","1996"],"dc:description":["A practical, general and efficient protocol for the catalytic epoxidation of alkenes has been developed. The in situ generation of reactive dioxiranes capable of epoxidizing a variety of alkenes under biphasic conditions has been accomplished using phase transfer catalysts bearing a carbonyl group. Optimal epoxidation conditions employ 10 mol % of 1-dodecyl-1-methyl-4-oxopiperidinium trifluoromethanesulfonate (9d$\\sp+$OTf$\\sp-)$ in a $\\rm CH\\sb2Cl\\sb2$/pH $7.5{-}8.0$ biphase using potassium monoperoxosulfate (Oxone) as the oxidant. Optimization of the conditions identified (1) slow addition rate, (2) pH 7.5-8.0, (3) n-dodecyl chain, and (4) the triflate salt as key experimental and structural variables.","Efforts to develop an asymmetric epoxidation of alkene protocol using chiral, non-racemic ketone promoters are also reported. Chlorodifluoroketone promoter 36 was synthesized in 13 steps and subjected to our standard epoxidation of alkenes system and resulted in complete conversion when the reaction solution was emulsified and a level of asymmetric induction of 14% ee.","Also described is a stereochemical study on the intramolecular hydrosilylation of $\\alpha,\\beta$-unsaturated esters. The intramolecular hydrosilylation of several 3-methyl-4-siloxy-2-butenoates afforded cis-disubstituted $\\gamma$-lactones after desilylation. The diastereoinduction was sensitive to the bulk of the allylic substituents, but not to the groups on silicon. The origin of asymmetric induction is believed to be the A$\\sp{1,2}$ strain from the $\\beta$-methyl group.","Made available in DSpace on 2011-05-07T12:11:06Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702514.pdf: 10992081 bytes, checksum: f33508f4ec3da65394ec3773cb111d61 (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:37:47Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:15:36-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["9780591087567","AAI9702514","(UMI)AAI9702514","http://hdl.handle.net/2142/19549"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Forbes, David Christopher"],"dc:subject":["Chemistry, Organic"],"dc:title":["Dioxirane-mediated epoxidation of alkenes: The development of catalytic and asymmetric protocols"],"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":"2026-07-22T22:25:14Z"}