{"id":{"repo_id":"ubc","oai_identifier":"oai:circle.library.ubc.ca:2429/1935"},"canonical_url":"https://search.dev.ndltd.org/etd/ubc/oai:circle.library.ubc.ca:2429/1935","repository":{"repo_id":"ubc","name":"University of British Columbia","base_url":"http://circle.library.ubc.ca/oai/request"},"display":{"title":"Evaluation of camphor derivatives in terpenoid synthesis","abstract":"New enantiospecific syntheses of 5,6-dehydrocamphor (36) and 5-methy1-5,6-dehydrocamphor (178) are reported, and these two compounds were evaluated as intermediates in terpenoid synthesis. Addition of an alkenyl unit to (+)-5,6-dehydro-camphor (36) and subsequent anionic oxy-Cope rearrangement of the resulting 1,5-diene (64) provided hydrindenone 66. Ring expansion of 66 provided decalin intermediate 69 which contains the A/B ring system common to many terpenoids; however, the stereo-specific introduction of an angular methyl group to provide a system such as 40 eludedus. Therefore, a similar synthetic strategy using (+5-methyl-5,6-dehydrocamphor (178)was investigated. Isopropenyl addition to 178 and subsequent anionic oxy-Copere arrangement provided hydrindenone 190 which contained the desired angular methyl group. (-)-5-Methyl-5,6-dehydrocamphor (178) was also converted to enone 204, but stereoselective conjugate addition to this enone (204) was not satisfactory. Addition of amore complex alkenyl unit to (-)-5-methyl-5,6-dehydrocamphor (178) provided 1,5-diene179, however, anionic oxy-Cope rearrangement to provide hydrindenone 180 did not occur, presumably due to steric effects. The first enantio selective synthesis of (-)-4-methylcamphor (229) is also reported. It is expected that 229 will undergo reactions analogous to those reported for camphor(25) and therefore would provide a route to trans hydrindenone 232. The latter compound is a potentially useful intermediate in the synthesis of the lanostane group of triterpenoids whereas its enantiomer (ent-232) derived from (+)-4-methylcamphor (ent-178) could gain access to the euphane group of triterpenoids.","abstract_html":"New enantiospecific syntheses of 5,6-dehydrocamphor (36) and 5-methy1-5,6-dehydrocamphor (178) are reported, and these two compounds were evaluated as intermediates in terpenoid synthesis. Addition of an alkenyl unit to (+)-5,6-dehydro-camphor (36) and subsequent anionic oxy-Cope rearrangement of the resulting 1,5-diene (64) provided hydrindenone 66. Ring expansion of 66 provided decalin intermediate 69 which contains the A/B ring system common to many terpenoids; however, the stereo-specific introduction of an angular methyl group to provide a system such as 40 eludedus. Therefore, a similar synthetic strategy using (+5-methyl-5,6-dehydrocamphor (178)was investigated. Isopropenyl addition to 178 and subsequent anionic oxy-Copere arrangement provided hydrindenone 190 which contained the desired angular methyl group. (-)-5-Methyl-5,6-dehydrocamphor (178) was also converted to enone 204, but stereoselective conjugate addition to this enone (204) was not satisfactory. Addition of amore complex alkenyl unit to (-)-5-methyl-5,6-dehydrocamphor (178) provided 1,5-diene179, however, anionic oxy-Cope rearrangement to provide hydrindenone 180 did not occur, presumably due to steric effects. The first enantio selective synthesis of (-)-4-methylcamphor (229) is also reported. It is expected that 229 will undergo reactions analogous to those reported for camphor(25) and therefore would provide a route to trans hydrindenone 232. The latter compound is a potentially useful intermediate in the synthesis of the lanostane group of triterpenoids whereas its enantiomer (ent-232) derived from (+)-4-methylcamphor (ent-178) could gain access to the euphane group of triterpenoids.","abstract_has_math":false,"creators":["Palme, Monica H."],"institution":"University of British Columbia","degree_name":"Doctor of Philosophy - PhD","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1993,"date_issued":"1993","date_published":"1993","updated_at":"2026-07-24T05:07:30Z","subjects":[],"languages":["eng"],"rights":["For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2429/1935","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Palme, Monica H."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1993"]},{"key":"dc:publisher","label":"Institution","values":["University of British Columbia"]},{"key":"dc:type","label":"Dc Type","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":["Doctor of Philosophy - PhD"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of British Columbia"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["For non-commercial purposes only, such as research, private study and education. 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Ring expansion of 66 provided decalin intermediate 69 which contains the A/B ring system common to many terpenoids; however, the stereo-specific introduction of an angular methyl group to provide a system such as 40 eludedus. Therefore, a similar synthetic strategy using (+5-methyl-5,6-dehydrocamphor (178)was investigated. Isopropenyl addition to 178 and subsequent anionic oxy-Copere arrangement provided hydrindenone 190 which contained the desired angular methyl group. (-)-5-Methyl-5,6-dehydrocamphor (178) was also converted to enone 204, but stereoselective conjugate addition to this enone (204) was not satisfactory. Addition of amore complex alkenyl unit to (-)-5-methyl-5,6-dehydrocamphor (178) provided 1,5-diene179, however, anionic oxy-Cope rearrangement to provide hydrindenone 180 did not occur, presumably due to steric effects. The first enantio selective synthesis of (-)-4-methylcamphor (229) is also reported. It is expected that 229 will undergo reactions analogous to those reported for camphor(25) and therefore would provide a route to trans hydrindenone 232. The latter compound is a potentially useful intermediate in the synthesis of the lanostane group of triterpenoids whereas its enantiomer (ent-232) derived from (+)-4-methylcamphor (ent-178) could gain access to the euphane group of triterpenoids."]},{"key":"dc:format","label":"Dc Format","values":["8088973","application/pdf"]},{"key":"dc:title","label":"Title","values":["Evaluation of camphor derivatives in terpenoid synthesis"]}]}],"canonical_facts":{"dc:creator":["Palme, Monica H."],"dc:date":["1993"],"dc:description":["New enantiospecific syntheses of 5,6-dehydrocamphor (36) and 5-methy1-5,6-dehydrocamphor (178) are reported, and these two compounds were evaluated as intermediates in terpenoid synthesis. Addition of an alkenyl unit to (+)-5,6-dehydro-camphor (36) and subsequent anionic oxy-Cope rearrangement of the resulting 1,5-diene (64) provided hydrindenone 66. Ring expansion of 66 provided decalin intermediate 69 which contains the A/B ring system common to many terpenoids; however, the stereo-specific introduction of an angular methyl group to provide a system such as 40 eludedus. Therefore, a similar synthetic strategy using (+5-methyl-5,6-dehydrocamphor (178)was investigated. Isopropenyl addition to 178 and subsequent anionic oxy-Copere arrangement provided hydrindenone 190 which contained the desired angular methyl group. (-)-5-Methyl-5,6-dehydrocamphor (178) was also converted to enone 204, but stereoselective conjugate addition to this enone (204) was not satisfactory. Addition of amore complex alkenyl unit to (-)-5-methyl-5,6-dehydrocamphor (178) provided 1,5-diene179, however, anionic oxy-Cope rearrangement to provide hydrindenone 180 did not occur, presumably due to steric effects. The first enantio selective synthesis of (-)-4-methylcamphor (229) is also reported. It is expected that 229 will undergo reactions analogous to those reported for camphor(25) and therefore would provide a route to trans hydrindenone 232. The latter compound is a potentially useful intermediate in the synthesis of the lanostane group of triterpenoids whereas its enantiomer (ent-232) derived from (+)-4-methylcamphor (ent-178) could gain access to the euphane group of triterpenoids."],"dc:format":["8088973","application/pdf"],"dc:identifier":["http://hdl.handle.net/2429/1935","http://circle.library.ubc.ca/bitstream/2429/1935/1/ubc_1993_spring_phd_palme_monica.pdf"],"dc:language":["eng"],"dc:publisher":["University of British Columbia"],"dc:rights":["For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use."],"dc:title":["Evaluation of camphor derivatives in terpenoid synthesis"],"dc:type":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy - PhD"],"thesis:institution_name":["University of British Columbia"]},"updated_at":"2026-07-24T05:07:30Z"}