{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:59018"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:59018","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Metal based asymmetric catalysis in Baeyer-Villiger oxidations","abstract":"One of the objectives of the present thesis was to improve the efficiency of an aluminium-catalyzed Baeyer-Villiger oxidation. This system was based on a mediating species formed by enantiopure 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) and Me2AlCl and utilized a hydroperoxide as oxidant. A first attempt towards an optimized version relied upon the modification of the substitution pattern of the binaphthyl ligand. The introduction of electron-withdrawing groups in position 6 and 6' of the binaphthyl scaffold had a positive influence on the enantioselectivity, affording lactones with up to 81% ee at full conversion. A further investigation was undertaken concerning the structure of the oxidant. Modest co-operative effects between the chiral ligand and a chiral hydroperoxide as a result of matched and mismatched combinations were observed. Moreover, a new asymmetric variant of the Baeyer-Villiger rearrangement was devised. The combination of enantiopure BINOL and properly chosen magnesium reagents gave rise to species that were able to mediate the oxidation of prochiral cyclobutanones to the corresponding butyrolactones in high yields and with modest to good enantioselectivity. It was also demonstrated that Baeyer-Villiger reactions can be performed efficiently in compressed CO2 at room temperature using the Mukaiyama system, i.e. oxygen as terminal oxidant and an aldehyde as co-reductant. For instance, cyclohexanone and norbornan-2-one reacted smoothly, yielding the corresponding lactones with 75% and 92% conversion, respectively","abstract_html":"One of the objectives of the present thesis was to improve the efficiency of an aluminium-catalyzed Baeyer-Villiger oxidation. This system was based on a mediating species formed by enantiopure 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) and Me2AlCl and utilized a hydroperoxide as oxidant. A first attempt towards an optimized version relied upon the modification of the substitution pattern of the binaphthyl ligand. The introduction of electron-withdrawing groups in position 6 and 6' of the binaphthyl scaffold had a positive influence on the enantioselectivity, affording lactones with up to 81% ee at full conversion. A further investigation was undertaken concerning the structure of the oxidant. Modest co-operative effects between the chiral ligand and a chiral hydroperoxide as a result of matched and mismatched combinations were observed. Moreover, a new asymmetric variant of the Baeyer-Villiger rearrangement was devised. The combination of enantiopure BINOL and properly chosen magnesium reagents gave rise to species that were able to mediate the oxidation of prochiral cyclobutanones to the corresponding butyrolactones in high yields and with modest to good enantioselectivity. It was also demonstrated that Baeyer-Villiger reactions can be performed efficiently in compressed CO2 at room temperature using the Mukaiyama system, i.e. oxygen as terminal oxidant and an aldehyde as co-reductant. For instance, cyclohexanone and norbornan-2-one reacted smoothly, yielding the corresponding lactones with 75% and 92% conversion, respectively","abstract_has_math":false,"creators":["Palazzi, Chiara"],"institution":"Publikationsserver der RWTH Aachen University","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Bolm, Carsten"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2002,"date_issued":"2002","date_published":"2002","updated_at":"2026-07-30T19:42:31Z","subjects":["info:eu-repo/classification/ddc/540","Bayer-Villiger-Oxidation","Asymmetrische Reaktion","Metallkomplexe","Chirale Verbindungen","Katalysator","Kohlendioxid","Überkitischer Zustand","Chemie","Asymmetrische Synthese","Homogene Katalyse"],"languages":["eng"],"rights":["info:eu-repo/semantics/openAccess"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120836%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120836%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120836%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/59018","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Bolm, Carsten"]},{"key":"dc:creator","label":"Author","values":["Palazzi, Chiara"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2002"]},{"key":"dc:publisher","label":"Institution","values":["Publikationsserver der RWTH Aachen University"]},{"key":"dc:relation","label":"Dc Relation","values":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-6409","info:eu-repo/semantics/altIdentifier/doi/10.18154/RWTH-CONV-120836"]},{"key":"dc:type","label":"Dc Type","values":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["info:eu-repo/classification/ddc/540","Bayer-Villiger-Oxidation","Asymmetrische Reaktion","Metallkomplexe","Chirale Verbindungen","Katalysator","Kohlendioxid","Überkitischer Zustand","Chemie","Asymmetrische Synthese","Homogene Katalyse"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["info:eu-repo/semantics/openAccess"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/record/59018","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120836%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["One of the objectives of the present thesis was to improve the efficiency of an aluminium-catalyzed Baeyer-Villiger oxidation. This system was based on a mediating species formed by enantiopure 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) and Me2AlCl and utilized a hydroperoxide as oxidant. A first attempt towards an optimized version relied upon the modification of the substitution pattern of the binaphthyl ligand. The introduction of electron-withdrawing groups in position 6 and 6' of the binaphthyl scaffold had a positive influence on the enantioselectivity, affording lactones with up to 81% ee at full conversion. A further investigation was undertaken concerning the structure of the oxidant. Modest co-operative effects between the chiral ligand and a chiral hydroperoxide as a result of matched and mismatched combinations were observed. Moreover, a new asymmetric variant of the Baeyer-Villiger rearrangement was devised. The combination of enantiopure BINOL and properly chosen magnesium reagents gave rise to species that were able to mediate the oxidation of prochiral cyclobutanones to the corresponding butyrolactones in high yields and with modest to good enantioselectivity. It was also demonstrated that Baeyer-Villiger reactions can be performed efficiently in compressed CO2 at room temperature using the Mukaiyama system, i.e. oxygen as terminal oxidant and an aldehyde as co-reductant. For instance, cyclohexanone and norbornan-2-one reacted smoothly, yielding the corresponding lactones with 75% and 92% conversion, respectively"]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University 157 S. : graph. Darst. (2002). doi:10.18154/RWTH-CONV-120836 = Aachen, Techn. Hochsch., Diss., 2002"]},{"key":"dc:title","label":"Title","values":["Metal based asymmetric catalysis in Baeyer-Villiger oxidations"]}]}],"canonical_facts":{"dc:contributor":["Bolm, Carsten"],"dc:coverage":["DE"],"dc:creator":["Palazzi, Chiara"],"dc:date":["2002"],"dc:description":["One of the objectives of the present thesis was to improve the efficiency of an aluminium-catalyzed Baeyer-Villiger oxidation. This system was based on a mediating species formed by enantiopure 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) and Me2AlCl and utilized a hydroperoxide as oxidant. A first attempt towards an optimized version relied upon the modification of the substitution pattern of the binaphthyl ligand. The introduction of electron-withdrawing groups in position 6 and 6' of the binaphthyl scaffold had a positive influence on the enantioselectivity, affording lactones with up to 81% ee at full conversion. A further investigation was undertaken concerning the structure of the oxidant. Modest co-operative effects between the chiral ligand and a chiral hydroperoxide as a result of matched and mismatched combinations were observed. Moreover, a new asymmetric variant of the Baeyer-Villiger rearrangement was devised. The combination of enantiopure BINOL and properly chosen magnesium reagents gave rise to species that were able to mediate the oxidation of prochiral cyclobutanones to the corresponding butyrolactones in high yields and with modest to good enantioselectivity. It was also demonstrated that Baeyer-Villiger reactions can be performed efficiently in compressed CO2 at room temperature using the Mukaiyama system, i.e. oxygen as terminal oxidant and an aldehyde as co-reductant. For instance, cyclohexanone and norbornan-2-one reacted smoothly, yielding the corresponding lactones with 75% and 92% conversion, respectively"],"dc:identifier":["https://publications.rwth-aachen.de/record/59018","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120836%22"],"dc:language":["eng"],"dc:publisher":["Publikationsserver der RWTH Aachen University"],"dc:relation":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-6409","info:eu-repo/semantics/altIdentifier/doi/10.18154/RWTH-CONV-120836"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University 157 S. : graph. Darst. (2002). doi:10.18154/RWTH-CONV-120836 = Aachen, Techn. 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