{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:60254"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:60254","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Asymmetrischer katalytischer Phenyltransfer zur Synthese von Diarylmethanolen und Diarylmethylaminen","abstract":"Enantiopure diarylmethanols and diarylmethylamines are important intermediates in the synthesis of biologically active compounds, since their derivatives have e. g. antihistaminic properties. For example, the (S)-enantiomer of the commercially important non-sedating antihistamine agent Cetirizine hydrochloride, a diarylmethylamine derivative, displays a better pharmacological profile than the racemate. Despite the importance of these compounds, asymmetric (catalytic) processes for the synthesis of diarylmethanols and especially diarylmethylamines are rather limited. For the synthesis of diarylmethanols, a highly enantioselective catalytic phenyl transfer from a mixed organozinc reagent to aldehydes was developed, employing catalytic amounts of a chiral catalyst precursor. The results of synthetic studies and investigations in order to reveal the nature of the active species in the catalysis by means of low-temperature-NMR- and IR-spectroscopic methods are presented. Previous syntheses of enantiopure diarylmethylamines relied on resolution, stoichiometric amounts of chromium or diastereoselective approaches via chiral auxiliaries. A highly enantioselective catalytic procedure for the addition of diphenylzinc to masked N-formyl-imines employing [2.2]-paracyclophane-based ketimines was developed and is described.","abstract_html":"Enantiopure diarylmethanols and diarylmethylamines are important intermediates in the synthesis of biologically active compounds, since their derivatives have e. g. antihistaminic properties. For example, the (S)-enantiomer of the commercially important non-sedating antihistamine agent Cetirizine hydrochloride, a diarylmethylamine derivative, displays a better pharmacological profile than the racemate. Despite the importance of these compounds, asymmetric (catalytic) processes for the synthesis of diarylmethanols and especially diarylmethylamines are rather limited. For the synthesis of diarylmethanols, a highly enantioselective catalytic phenyl transfer from a mixed organozinc reagent to aldehydes was developed, employing catalytic amounts of a chiral catalyst precursor. The results of synthetic studies and investigations in order to reveal the nature of the active species in the catalysis by means of low-temperature-NMR- and IR-spectroscopic methods are presented. Previous syntheses of enantiopure diarylmethylamines relied on resolution, stoichiometric amounts of chromium or diastereoselective approaches via chiral auxiliaries. A highly enantioselective catalytic procedure for the addition of diphenylzinc to masked N-formyl-imines employing [2.2]-paracyclophane-based ketimines was developed and is described.","abstract_has_math":false,"creators":["Hermanns, Nina"],"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":"2026-07-30T19:42:56Z","subjects":["info:eu-repo/classification/ddc/540","Chemie","Arylierung","Asymmetrische Synthese","Homogene Katalyse","Zinkorganyle","Diarylmethanole","Diarylmethylamine","Metallocene"],"languages":["ger"],"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-121977%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121977%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121977%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/60254","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":["Hermanns, Nina"]}]},{"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-4707"]},{"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","Chemie","Arylierung","Asymmetrische Synthese","Homogene Katalyse","Zinkorganyle","Diarylmethanole","Diarylmethylamine","Metallocene"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["ger"]},{"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/60254","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121977%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Enantiopure diarylmethanols and diarylmethylamines are important intermediates in the synthesis of biologically active compounds, since their derivatives have e. g. antihistaminic properties. For example, the (S)-enantiomer of the commercially important non-sedating antihistamine agent Cetirizine hydrochloride, a diarylmethylamine derivative, displays a better pharmacological profile than the racemate. Despite the importance of these compounds, asymmetric (catalytic) processes for the synthesis of diarylmethanols and especially diarylmethylamines are rather limited. For the synthesis of diarylmethanols, a highly enantioselective catalytic phenyl transfer from a mixed organozinc reagent to aldehydes was developed, employing catalytic amounts of a chiral catalyst precursor. The results of synthetic studies and investigations in order to reveal the nature of the active species in the catalysis by means of low-temperature-NMR- and IR-spectroscopic methods are presented. Previous syntheses of enantiopure diarylmethylamines relied on resolution, stoichiometric amounts of chromium or diastereoselective approaches via chiral auxiliaries. A highly enantioselective catalytic procedure for the addition of diphenylzinc to masked N-formyl-imines employing [2.2]-paracyclophane-based ketimines was developed and is described."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University 169 S. (2002). = Aachen, Techn. Hochsch., Diss., 2002"]},{"key":"dc:title","label":"Title","values":["Asymmetrischer katalytischer Phenyltransfer zur Synthese von Diarylmethanolen und Diarylmethylaminen"]}]}],"canonical_facts":{"dc:contributor":["Bolm, Carsten"],"dc:coverage":["DE"],"dc:creator":["Hermanns, Nina"],"dc:date":["2002"],"dc:description":["Enantiopure diarylmethanols and diarylmethylamines are important intermediates in the synthesis of biologically active compounds, since their derivatives have e. g. antihistaminic properties. 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A highly enantioselective catalytic procedure for the addition of diphenylzinc to masked N-formyl-imines employing [2.2]-paracyclophane-based ketimines was developed and is described."],"dc:identifier":["https://publications.rwth-aachen.de/record/60254","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-121977%22"],"dc:language":["ger"],"dc:publisher":["Publikationsserver der RWTH Aachen University"],"dc:relation":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-4707"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University 169 S. (2002). = Aachen, Techn. 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