{"id":{"repo_id":"ottawa-retro","oai_identifier":"oai:ruor.uottawa.ca:10393/9177"},"canonical_url":"https://search.dev.ndltd.org/etd/ottawa-retro/oai:ruor.uottawa.ca:10393/9177","repository":{"repo_id":"ottawa-retro","name":"University of Ottawa","base_url":"https://ruor.uottawa.ca/server/oai/request"},"display":{"title":"Carbomagnesium mediated reactions: A versatile tool in organic synthesis.","abstract":"Magnesium-mediated carbometallation has been employed as a route to a diverse range of organic synthons. The original carbometallation procedure has been optimized by a solvent study, which indicates that cyclohexane can be used in most cases, to improve the yields and consistency of the reaction. A wide-range of polysubstituted furans (232) were obtained when the reaction intermediate (144) was quenched with either dimethylformamide or benzonitrile. The use of carbon dioxide as an electrophile, provided a short (two-steps) synthesis of the Merck anti-inflammatory drug, Vioxx RTM (231). The reaction was also extended to a direct one-step synthesis of the ene-diyne chromophore (186). Additional research afforded a versatile route from 144 to dienophiles for intramolecular Diels-Alder reactions. An expedient route to the Taxol A/B-ring system (329) was developed. This ring system underwent a facile enone accelerated Cope rearrangement to generate a bicylco[2.2.2]octanone ring system (330). Finally, the dienophiles prepared from the carbomagnesiation reaction were employed as key steps in the preparation of tether controlled intramolecular Diels-Alder reactions. The reactions were shown to be more facile when cis-isopropylidene acetals ( 386) were employed in the tether. The trans-isopropylidene acetal tether (385b) was also prepared for a direct comparison. As anticipated the cycloaddition occurred at a much slower rate.* *Please refer to dissertation for diagrams.","abstract_html":"Magnesium-mediated carbometallation has been employed as a route to a diverse range of organic synthons. The original carbometallation procedure has been optimized by a solvent study, which indicates that cyclohexane can be used in most cases, to improve the yields and consistency of the reaction. A wide-range of polysubstituted furans (232) were obtained when the reaction intermediate (144) was quenched with either dimethylformamide or benzonitrile. The use of carbon dioxide as an electrophile, provided a short (two-steps) synthesis of the Merck anti-inflammatory drug, Vioxx RTM (231). The reaction was also extended to a direct one-step synthesis of the ene-diyne chromophore (186). Additional research afforded a versatile route from 144 to dienophiles for intramolecular Diels-Alder reactions. An expedient route to the Taxol A/B-ring system (329) was developed. This ring system underwent a facile enone accelerated Cope rearrangement to generate a bicylco[2.2.2]octanone ring system (330). Finally, the dienophiles prepared from the carbomagnesiation reaction were employed as key steps in the preparation of tether controlled intramolecular Diels-Alder reactions. The reactions were shown to be more facile when cis-isopropylidene acetals ( 386) were employed in the tether. The trans-isopropylidene acetal tether (385b) was also prepared for a direct comparison. As anticipated the cycloaddition occurred at a much slower rate.* *Please refer to dissertation for diagrams.","abstract_has_math":false,"creators":["Forgione, Pat."],"institution":"University of Ottawa (Canada)","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Fallis, Alex G.,"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-03-23T18:22:06Z","date_published":"2009-03-23T18:22:06Z","updated_at":"2026-07-24T03:39:36Z","subjects":["Chemistry, Organic."],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 63-04, Section: B, page: 1846.","9780612672154","http://dx.doi.org/10.20381/ruor-16185"],"render_values":[{"text":"Source: Dissertation Abstracts International, Volume: 63-04, Section: B, page: 1846.","href":null,"code":true},{"text":"9780612672154","href":null,"code":true},{"text":"http://dx.doi.org/10.20381/ruor-16185","href":"http://dx.doi.org/10.20381/ruor-16185","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10393/9177","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Fallis, Alex G.,"]},{"key":"dc:creator","label":"Author","values":["Forgione, Pat."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-03-23T18:22:06Z","2001"]},{"key":"dc:publisher","label":"Institution","values":["University of Ottawa (Canada)"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["Source: Dissertation Abstracts International, Volume: 63-04, Section: B, page: 1846.","9780612672154","http://hdl.handle.net/10393/9177","http://dx.doi.org/10.20381/ruor-16185"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Magnesium-mediated carbometallation has been employed as a route to a diverse range of organic synthons. The original carbometallation procedure has been optimized by a solvent study, which indicates that cyclohexane can be used in most cases, to improve the yields and consistency of the reaction. A wide-range of polysubstituted furans (232) were obtained when the reaction intermediate (144) was quenched with either dimethylformamide or benzonitrile. The use of carbon dioxide as an electrophile, provided a short (two-steps) synthesis of the Merck anti-inflammatory drug, Vioxx RTM (231). The reaction was also extended to a direct one-step synthesis of the ene-diyne chromophore (186). Additional research afforded a versatile route from 144 to dienophiles for intramolecular Diels-Alder reactions. An expedient route to the Taxol A/B-ring system (329) was developed. This ring system underwent a facile enone accelerated Cope rearrangement to generate a bicylco[2.2.2]octanone ring system (330). Finally, the dienophiles prepared from the carbomagnesiation reaction were employed as key steps in the preparation of tether controlled intramolecular Diels-Alder reactions. The reactions were shown to be more facile when cis-isopropylidene acetals ( 386) were employed in the tether. The trans-isopropylidene acetal tether (385b) was also prepared for a direct comparison. As anticipated the cycloaddition occurred at a much slower rate.* *Please refer to dissertation for diagrams."]},{"key":"dc:format","label":"Dc Format","values":["225 p.","application/pdf"]},{"key":"dc:title","label":"Title","values":["Carbomagnesium mediated reactions: A versatile tool in organic synthesis."]}]}],"canonical_facts":{"dc:contributor":["Fallis, Alex G.,"],"dc:creator":["Forgione, Pat."],"dc:date":["2009-03-23T18:22:06Z","2001"],"dc:description":["Magnesium-mediated carbometallation has been employed as a route to a diverse range of organic synthons. The original carbometallation procedure has been optimized by a solvent study, which indicates that cyclohexane can be used in most cases, to improve the yields and consistency of the reaction. A wide-range of polysubstituted furans (232) were obtained when the reaction intermediate (144) was quenched with either dimethylformamide or benzonitrile. The use of carbon dioxide as an electrophile, provided a short (two-steps) synthesis of the Merck anti-inflammatory drug, Vioxx RTM (231). The reaction was also extended to a direct one-step synthesis of the ene-diyne chromophore (186). Additional research afforded a versatile route from 144 to dienophiles for intramolecular Diels-Alder reactions. An expedient route to the Taxol A/B-ring system (329) was developed. This ring system underwent a facile enone accelerated Cope rearrangement to generate a bicylco[2.2.2]octanone ring system (330). Finally, the dienophiles prepared from the carbomagnesiation reaction were employed as key steps in the preparation of tether controlled intramolecular Diels-Alder reactions. The reactions were shown to be more facile when cis-isopropylidene acetals ( 386) were employed in the tether. The trans-isopropylidene acetal tether (385b) was also prepared for a direct comparison. As anticipated the cycloaddition occurred at a much slower rate.* *Please refer to dissertation for diagrams."],"dc:format":["225 p.","application/pdf"],"dc:identifier":["Source: Dissertation Abstracts International, Volume: 63-04, Section: B, page: 1846.","9780612672154","http://hdl.handle.net/10393/9177","http://dx.doi.org/10.20381/ruor-16185"],"dc:publisher":["University of Ottawa (Canada)"],"dc:subject":["Chemistry, Organic."],"dc:title":["Carbomagnesium mediated reactions: A versatile tool in organic synthesis."],"dc:type":["Thesis"]},"updated_at":"2026-07-24T03:39:36Z"}