{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:50476"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:50476","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Asymmetric synthesis of medium-sized carbocycles spirocycles and oxabicycles via ring closing metathesis sufoximine substituted trienes and dihydropyran derivates","abstract":"The synthesis of substituted chiral medium-sized carbocycles is an important goal of organic synthesis. Ring-closing metathesis of acyclic dienes is a very effective method for the synthesis of medium-sized carbocycles. In this project, sulfoximine-substituted trienes were proven to be excellent parent compounds for the selective synthesis of Z-configured medium sized carbocycles. The formation of sulfoximine-substituted trienes, key intermediates of the described synthesis, was accomplished via a-functionalization of the corresponding sulfoximine-substituted homoallylic alcohols, whereby several protocols were developed. With the spectrum of sulfoximine-substituted trienes at hand, we investigated their RCM. Thus, the products of a-functionalization described above were treated with Grubbs second generation catalyst to give the desired carbocycles in very good yields. Interestingly, all carbocycles were obtained exclusively as Z-configured isomers, only in the case of the 11-membered carbocycle formation of a small amount of E-configured isomer was observed. Finally, sulfoximine moiety was removed from carbocycles. In the case of seven-membered carbocycle methyl group was introduced via cross-coupling reaction with methyl cuprate. The nine membered carbocycle was treated with aluminium amalgam to give corresponding carbocycle without sulfoximine-moiety. Sulfoximine-mediated strategy was also applied to a synthesis of spirocyclic and oxabicyclic compounds. The key compounds of our synthesis were the sulfoximine-substituted pyrans, which served as parent compounds for spiroketals, spiroethers and oxabicycles. Spiroketals and spiroethers were synthesized via introduction of a suitable substituent in the a-position of pyrans followed by RCM. Chloride-substituted spiroethers were synthesized via the Prins reaction of the corresponding sulfoximine –substituted pyrans bearing 1-pentenyl substituent. The synthesis of pyrans was accomplished via deprotection-cyclization of the corresponding a-sulfoximido ketones.","abstract_html":"The synthesis of substituted chiral medium-sized carbocycles is an important goal of organic synthesis. Ring-closing metathesis of acyclic dienes is a very effective method for the synthesis of medium-sized carbocycles. In this project, sulfoximine-substituted trienes were proven to be excellent parent compounds for the selective synthesis of Z-configured medium sized carbocycles. The formation of sulfoximine-substituted trienes, key intermediates of the described synthesis, was accomplished via a-functionalization of the corresponding sulfoximine-substituted homoallylic alcohols, whereby several protocols were developed. With the spectrum of sulfoximine-substituted trienes at hand, we investigated their RCM. Thus, the products of a-functionalization described above were treated with Grubbs second generation catalyst to give the desired carbocycles in very good yields. Interestingly, all carbocycles were obtained exclusively as Z-configured isomers, only in the case of the 11-membered carbocycle formation of a small amount of E-configured isomer was observed. Finally, sulfoximine moiety was removed from carbocycles. In the case of seven-membered carbocycle methyl group was introduced via cross-coupling reaction with methyl cuprate. The nine membered carbocycle was treated with aluminium amalgam to give corresponding carbocycle without sulfoximine-moiety. Sulfoximine-mediated strategy was also applied to a synthesis of spirocyclic and oxabicyclic compounds. The key compounds of our synthesis were the sulfoximine-substituted pyrans, which served as parent compounds for spiroketals, spiroethers and oxabicycles. Spiroketals and spiroethers were synthesized via introduction of a suitable substituent in the a-position of pyrans followed by RCM. Chloride-substituted spiroethers were synthesized via the Prins reaction of the corresponding sulfoximine –substituted pyrans bearing 1-pentenyl substituent. The synthesis of pyrans was accomplished via deprotection-cyclization of the corresponding a-sulfoximido ketones.","abstract_has_math":false,"creators":["Lejkowski, Michal"],"institution":"Publikationsserver der RWTH Aachen University","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Gais, Hans-Joachim"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008","date_published":"2008","updated_at":"2026-07-30T19:40:25Z","subjects":["info:eu-repo/classification/ddc/540","Organische Chemie","Asymmetrische Synthese","Carbocyclen","Chemie","Spirocyclen","Sulfoximin","Ring-Schluss-Metathese","asymmetric synthesis","medium-sized carbocycles","spirocycles","ring-closing metathesis"],"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-113019%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-113019%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-113019%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/50476","outbound_label":"Repository record","outbound_source":"dc:identifier"},"source_record":{"url":"https://publications.rwth-aachen.de/oai2d?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Apublications.rwth-aachen.de%3A50476","prefix":"oai_dc"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gais, Hans-Joachim"]},{"key":"dc:creator","label":"Author","values":["Lejkowski, Michal"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2008"]},{"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-26319"]},{"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","Organische Chemie","Asymmetrische Synthese","Carbocyclen","Chemie","Spirocyclen","Sulfoximin","Ring-Schluss-Metathese","asymmetric synthesis","medium-sized carbocycles","spirocycles","ring-closing metathesis"]}]},{"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/50476","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-113019%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The synthesis of substituted chiral medium-sized carbocycles is an important goal of organic synthesis. Ring-closing metathesis of acyclic dienes is a very effective method for the synthesis of medium-sized carbocycles. In this project, sulfoximine-substituted trienes were proven to be excellent parent compounds for the selective synthesis of Z-configured medium sized carbocycles. The formation of sulfoximine-substituted trienes, key intermediates of the described synthesis, was accomplished via a-functionalization of the corresponding sulfoximine-substituted homoallylic alcohols, whereby several protocols were developed. With the spectrum of sulfoximine-substituted trienes at hand, we investigated their RCM. Thus, the products of a-functionalization described above were treated with Grubbs second generation catalyst to give the desired carbocycles in very good yields. Interestingly, all carbocycles were obtained exclusively as Z-configured isomers, only in the case of the 11-membered carbocycle formation of a small amount of E-configured isomer was observed. Finally, sulfoximine moiety was removed from carbocycles. In the case of seven-membered carbocycle methyl group was introduced via cross-coupling reaction with methyl cuprate. The nine membered carbocycle was treated with aluminium amalgam to give corresponding carbocycle without sulfoximine-moiety. Sulfoximine-mediated strategy was also applied to a synthesis of spirocyclic and oxabicyclic compounds. The key compounds of our synthesis were the sulfoximine-substituted pyrans, which served as parent compounds for spiroketals, spiroethers and oxabicycles. Spiroketals and spiroethers were synthesized via introduction of a suitable substituent in the a-position of pyrans followed by RCM. Chloride-substituted spiroethers were synthesized via the Prins reaction of the corresponding sulfoximine –substituted pyrans bearing 1-pentenyl substituent. The synthesis of pyrans was accomplished via deprotection-cyclization of the corresponding a-sulfoximido ketones."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University 285 S. (2008). = Aachen, Techn. Hochsch., Diss., 2008"]},{"key":"dc:title","label":"Title","values":["Asymmetric synthesis of medium-sized carbocycles spirocycles and oxabicycles via ring closing metathesis sufoximine substituted trienes and dihydropyran derivates"]}]}],"canonical_facts":{"dc:contributor":["Gais, Hans-Joachim"],"dc:coverage":["DE"],"dc:creator":["Lejkowski, Michal"],"dc:date":["2008"],"dc:description":["The synthesis of substituted chiral medium-sized carbocycles is an important goal of organic synthesis. Ring-closing metathesis of acyclic dienes is a very effective method for the synthesis of medium-sized carbocycles. In this project, sulfoximine-substituted trienes were proven to be excellent parent compounds for the selective synthesis of Z-configured medium sized carbocycles. The formation of sulfoximine-substituted trienes, key intermediates of the described synthesis, was accomplished via a-functionalization of the corresponding sulfoximine-substituted homoallylic alcohols, whereby several protocols were developed. With the spectrum of sulfoximine-substituted trienes at hand, we investigated their RCM. Thus, the products of a-functionalization described above were treated with Grubbs second generation catalyst to give the desired carbocycles in very good yields. Interestingly, all carbocycles were obtained exclusively as Z-configured isomers, only in the case of the 11-membered carbocycle formation of a small amount of E-configured isomer was observed. Finally, sulfoximine moiety was removed from carbocycles. In the case of seven-membered carbocycle methyl group was introduced via cross-coupling reaction with methyl cuprate. The nine membered carbocycle was treated with aluminium amalgam to give corresponding carbocycle without sulfoximine-moiety. Sulfoximine-mediated strategy was also applied to a synthesis of spirocyclic and oxabicyclic compounds. The key compounds of our synthesis were the sulfoximine-substituted pyrans, which served as parent compounds for spiroketals, spiroethers and oxabicycles. Spiroketals and spiroethers were synthesized via introduction of a suitable substituent in the a-position of pyrans followed by RCM. Chloride-substituted spiroethers were synthesized via the Prins reaction of the corresponding sulfoximine –substituted pyrans bearing 1-pentenyl substituent. The synthesis of pyrans was accomplished via deprotection-cyclization of the corresponding a-sulfoximido ketones."],"dc:identifier":["https://publications.rwth-aachen.de/record/50476","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-113019%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-26319"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University 285 S. (2008). = Aachen, Techn. Hochsch., Diss., 2008"],"dc:subject":["info:eu-repo/classification/ddc/540","Organische Chemie","Asymmetrische Synthese","Carbocyclen","Chemie","Spirocyclen","Sulfoximin","Ring-Schluss-Metathese","asymmetric synthesis","medium-sized carbocycles","spirocycles","ring-closing metathesis"],"dc:title":["Asymmetric synthesis of medium-sized carbocycles spirocycles and oxabicycles via ring closing metathesis sufoximine substituted trienes and dihydropyran derivates"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:40:25Z"}