{"id":{"repo_id":"sask","oai_identifier":"oai:harvest.usask.ca:10388/etd-10312007-165406"},"canonical_url":"https://search.dev.ndltd.org/etd/sask/oai:harvest.usask.ca:10388/etd-10312007-165406","repository":{"repo_id":"sask","name":"University of Saskatchewan","base_url":"https://harvest.usask.ca/server/oai/request"},"display":{"title":"Chemistry with chiral lithium amides: enantiotopic group and face-selective reactions","abstract":"The accomplishment of the γ-alkylation reaction from β-keto esters of tropinone and the enantioselective aziridine formation from nortropinone is first reported. This opened two new paths to develop tropinone enolate chemistry. One is indirect α-alkylation of tropinone, another is the nucleophilic attack from α-C enolate to the nitrogen atom. Seven interesting chiral amines have been synthesized and applied into the enolate chemistry of two interesting precursors of synthesis of natural products: 1,4- cyclohexanedione monoethylene ketal and tropinone.The aldol reaction between the lithium enolate of 1,4-cyclohexanedione monoethylene ketal and benzaldehyde demonstrated the high diastereoselectivity (up to 98% de) and the moderate to high enantioselectivity (up to 75% ee) induced by those chiral lithium amides. On the other hand, high diastereoselectivity (up to 100% de) and the low enantioselectivity were obtained from the aldol reaction of tropinone enolate with benzaldehyde differentiated by chiral lithium amides with extra electron donor atoms. An analysis method to determine enantioselectivity from racemic α-hydroxytropinone was developed. That will, no doubt, benefit the further enantioselective α-hydroxylation reaction of tropinone.","abstract_html":"The accomplishment of the γ-alkylation reaction from β-keto esters of tropinone and the enantioselective aziridine formation from nortropinone is first reported. This opened two new paths to develop tropinone enolate chemistry. One is indirect α-alkylation of tropinone, another is the nucleophilic attack from α-C enolate to the nitrogen atom. Seven interesting chiral amines have been synthesized and applied into the enolate chemistry of two interesting precursors of synthesis of natural products: 1,4- cyclohexanedione monoethylene ketal and tropinone.The aldol reaction between the lithium enolate of 1,4-cyclohexanedione monoethylene ketal and benzaldehyde demonstrated the high diastereoselectivity (up to 98% de) and the moderate to high enantioselectivity (up to 75% ee) induced by those chiral lithium amides. On the other hand, high diastereoselectivity (up to 100% de) and the low enantioselectivity were obtained from the aldol reaction of tropinone enolate with benzaldehyde differentiated by chiral lithium amides with extra electron donor atoms. An analysis method to determine enantioselectivity from racemic α-hydroxytropinone was developed. That will, no doubt, benefit the further enantioselective α-hydroxylation reaction of tropinone.","abstract_has_math":false,"creators":["Wang, Li"],"institution":"University of Saskatchewan","degree_name":"Master of Science (M.Sc.)","degree_level":"Masters","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Majewski, Marek"],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007","date_published":"2007","updated_at":"2026-07-24T04:27:16Z","subjects":["lithium amide","Enantiotopic group&face selective"],"languages":["en_US"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10388/etd-10312007-165406","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Majewski, Marek"]},{"key":"dc:creator","label":"Author","values":["Wang, Li"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2007-10-31T16:54:06Z","2013-01-04T05:07:29Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2008-12-03T08:00:00Z","2013-01-04T05:07:29Z"]},{"key":"dc:date.issued","label":"Date","values":["2007"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science (M.Sc.)"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Saskatchewan"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["lithium amide","Enantiotopic group&face selective"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_US"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10388/etd-10312007-165406"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The accomplishment of the γ-alkylation reaction from β-keto esters of tropinone and the enantioselective aziridine formation from nortropinone is first reported. This opened two new paths to develop tropinone enolate chemistry. One is indirect α-alkylation of tropinone, another is the nucleophilic attack from α-C enolate to the nitrogen atom. Seven interesting chiral amines have been synthesized and applied into the enolate chemistry of two interesting precursors of synthesis of natural products: 1,4- cyclohexanedione monoethylene ketal and tropinone.The aldol reaction between the lithium enolate of 1,4-cyclohexanedione monoethylene ketal and benzaldehyde demonstrated the high diastereoselectivity (up to 98% de) and the moderate to high enantioselectivity (up to 75% ee) induced by those chiral lithium amides. On the other hand, high diastereoselectivity (up to 100% de) and the low enantioselectivity were obtained from the aldol reaction of tropinone enolate with benzaldehyde differentiated by chiral lithium amides with extra electron donor atoms. An analysis method to determine enantioselectivity from racemic α-hydroxytropinone was developed. That will, no doubt, benefit the further enantioselective α-hydroxylation reaction of tropinone."]},{"key":"dc:title","label":"Title","values":["Chemistry with chiral lithium amides: enantiotopic group and face-selective reactions"]}]}],"canonical_facts":{"dc:contributor.advisor":["Majewski, Marek"],"dc:creator":["Wang, Li"],"dc:date.accessioned":["2007-10-31T16:54:06Z","2013-01-04T05:07:29Z"],"dc:date.available":["2008-12-03T08:00:00Z","2013-01-04T05:07:29Z"],"dc:date.issued":["2007"],"dc:description.abstract":["The accomplishment of the γ-alkylation reaction from β-keto esters of tropinone and the enantioselective aziridine formation from nortropinone is first reported. This opened two new paths to develop tropinone enolate chemistry. One is indirect α-alkylation of tropinone, another is the nucleophilic attack from α-C enolate to the nitrogen atom. Seven interesting chiral amines have been synthesized and applied into the enolate chemistry of two interesting precursors of synthesis of natural products: 1,4- cyclohexanedione monoethylene ketal and tropinone.The aldol reaction between the lithium enolate of 1,4-cyclohexanedione monoethylene ketal and benzaldehyde demonstrated the high diastereoselectivity (up to 98% de) and the moderate to high enantioselectivity (up to 75% ee) induced by those chiral lithium amides. On the other hand, high diastereoselectivity (up to 100% de) and the low enantioselectivity were obtained from the aldol reaction of tropinone enolate with benzaldehyde differentiated by chiral lithium amides with extra electron donor atoms. An analysis method to determine enantioselectivity from racemic α-hydroxytropinone was developed. That will, no doubt, benefit the further enantioselective α-hydroxylation reaction of tropinone."],"dc:identifier.uri":["https://hdl.handle.net/10388/etd-10312007-165406"],"dc:language.iso":["en_US"],"dc:subject":["lithium amide","Enantiotopic group&face selective"],"dc:title":["Chemistry with chiral lithium amides: enantiotopic group and face-selective reactions"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Masters"],"thesis:degree_name":["Master of Science (M.Sc.)"],"thesis:institution_name":["University of Saskatchewan"]},"updated_at":"2026-07-24T04:27:16Z"}