{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84390"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84390","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part I. Solvolysis of Caryophyllen-8-Yl Derivatives: Model Reactions for Presilphiperfolanol Biogenesis. Part II. Stereochemistry of Lithium-Amine Reductions of Tetrasubstituted Epoxides and Phenylthiohydrins to Tertiary Alcohols","abstract":"A comparative study of the Li-amine reductions of model bicyclic tetrasubstituted epoxides and the corresponding trans-phenylthiohydrins was carried out to determine the stereochemistry and optimal reaction conditions for this transformation. Octalin, hydrindene, and bicyclo (3.3.0) octene epoxides were synthesized, and the product ratios from their reductions in NH$\\sb3$ and EtNH$\\sb2$ were determined and compared with those in ethylenediamine reported in the literature. Li-NH$\\sb3$ reductions gave best selectivities. Li-EtNH$\\sb2$ reductions were faster than Li-NH$\\sb3$ reductions, and they showed selectivities comparable to those with Li-ethylenediamine reported. trans-1,2-Phenylthiohydrins of octalin, hydrindene, and bicyclo (3.3.0) octene were synthesized by ring opening of the corresponding epoxides with Et$\\sb2$AlSPh. The reductions of the phenylthiohydrins and their respective phenylthioalkoxides were carried out in Li-NH$\\sb3,$ and the product ratios were determined. The potential for regioselective ring opening of epoxides combined with the ease of reduction of phenylthiohydrins, and the selectivity of Li-amine reductions to give a thermodynamic distribution of alcohols makes this method very appealing.","abstract_html":"A comparative study of the Li-amine reductions of model bicyclic tetrasubstituted epoxides and the corresponding trans-phenylthiohydrins was carried out to determine the stereochemistry and optimal reaction conditions for this transformation. Octalin, hydrindene, and bicyclo (3.3.0) octene epoxides were synthesized, and the product ratios from their reductions in NH$\\sb3$ and EtNH$\\sb2$ were determined and compared with those in ethylenediamine reported in the literature. Li-NH$\\sb3$ reductions gave best selectivities. Li-EtNH$\\sb2$ reductions were faster than Li-NH$\\sb3$ reductions, and they showed selectivities comparable to those with Li-ethylenediamine reported. trans-1,2-Phenylthiohydrins of octalin, hydrindene, and bicyclo (3.3.0) octene were synthesized by ring opening of the corresponding epoxides with Et$\\sb2$AlSPh. The reductions of the phenylthiohydrins and their respective phenylthioalkoxides were carried out in Li-NH$\\sb3,$ and the product ratios were determined. The potential for regioselective ring opening of epoxides combined with the ease of reduction of phenylthiohydrins, and the selectivity of Li-amine reductions to give a thermodynamic distribution of alcohols makes this method very appealing.","abstract_has_math":true,"creators":["Shankar, Sriram"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Coates, R.M."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:16Z","date_published":"2015-09-25T22:14:16Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9812766"],"render_values":[{"text":"(MiAaPQ)AAI9812766","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84390","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Coates, R.M."]},{"key":"dc:creator","label":"Author","values":["Shankar, Sriram"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:16Z","10000-01-01","1997"]},{"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"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84390","(MiAaPQ)AAI9812766"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A comparative study of the Li-amine reductions of model bicyclic tetrasubstituted epoxides and the corresponding trans-phenylthiohydrins was carried out to determine the stereochemistry and optimal reaction conditions for this transformation. Octalin, hydrindene, and bicyclo (3.3.0) octene epoxides were synthesized, and the product ratios from their reductions in NH$\\sb3$ and EtNH$\\sb2$ were determined and compared with those in ethylenediamine reported in the literature. Li-NH$\\sb3$ reductions gave best selectivities. Li-EtNH$\\sb2$ reductions were faster than Li-NH$\\sb3$ reductions, and they showed selectivities comparable to those with Li-ethylenediamine reported. trans-1,2-Phenylthiohydrins of octalin, hydrindene, and bicyclo (3.3.0) octene were synthesized by ring opening of the corresponding epoxides with Et$\\sb2$AlSPh. The reductions of the phenylthiohydrins and their respective phenylthioalkoxides were carried out in Li-NH$\\sb3,$ and the product ratios were determined. The potential for regioselective ring opening of epoxides combined with the ease of reduction of phenylthiohydrins, and the selectivity of Li-amine reductions to give a thermodynamic distribution of alcohols makes this method very appealing.","Made available in DSpace on 2015-09-25T22:14:16Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9812766.pdf: 9005342 bytes, checksum: 94e4c0eca0dbe2fbddb31ffa0b69c0ae (MD5) Previous issue date: 1997","Embargo set by: Seth Robbins for item 85671 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","212 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1997."]},{"key":"dc:title","label":"Title","values":["Part I. Solvolysis of Caryophyllen-8-Yl Derivatives: Model Reactions for Presilphiperfolanol Biogenesis. Part II. Stereochemistry of Lithium-Amine Reductions of Tetrasubstituted Epoxides and Phenylthiohydrins to Tertiary Alcohols"]}]}],"canonical_facts":{"dc:contributor":["Coates, R.M."],"dc:creator":["Shankar, Sriram"],"dc:date":["2015-09-25T22:14:16Z","10000-01-01","1997"],"dc:description":["A comparative study of the Li-amine reductions of model bicyclic tetrasubstituted epoxides and the corresponding trans-phenylthiohydrins was carried out to determine the stereochemistry and optimal reaction conditions for this transformation. Octalin, hydrindene, and bicyclo (3.3.0) octene epoxides were synthesized, and the product ratios from their reductions in NH$\\sb3$ and EtNH$\\sb2$ were determined and compared with those in ethylenediamine reported in the literature. Li-NH$\\sb3$ reductions gave best selectivities. Li-EtNH$\\sb2$ reductions were faster than Li-NH$\\sb3$ reductions, and they showed selectivities comparable to those with Li-ethylenediamine reported. trans-1,2-Phenylthiohydrins of octalin, hydrindene, and bicyclo (3.3.0) octene were synthesized by ring opening of the corresponding epoxides with Et$\\sb2$AlSPh. The reductions of the phenylthiohydrins and their respective phenylthioalkoxides were carried out in Li-NH$\\sb3,$ and the product ratios were determined. The potential for regioselective ring opening of epoxides combined with the ease of reduction of phenylthiohydrins, and the selectivity of Li-amine reductions to give a thermodynamic distribution of alcohols makes this method very appealing.","Made available in DSpace on 2015-09-25T22:14:16Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9812766.pdf: 9005342 bytes, checksum: 94e4c0eca0dbe2fbddb31ffa0b69c0ae (MD5) Previous issue date: 1997","Embargo set by: Seth Robbins for item 85671 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","212 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1997."],"dc:identifier":["http://hdl.handle.net/2142/84390","(MiAaPQ)AAI9812766"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["Part I. Solvolysis of Caryophyllen-8-Yl Derivatives: Model Reactions for Presilphiperfolanol Biogenesis. Part II. Stereochemistry of Lithium-Amine Reductions of Tetrasubstituted Epoxides and Phenylthiohydrins to Tertiary Alcohols"],"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":"2026-07-22T22:26:23Z"}