{"id":{"repo_id":"uic","oai_identifier":"oai:figshare.com:article/32994977"},"canonical_url":"https://search.dev.ndltd.org/etd/uic/oai:figshare.com:article/32994977","repository":{"repo_id":"uic","name":"University of Illinois - Chicago","base_url":"https://api.figshare.com/v2/oai"},"display":{"title":"Synthesis, Vinylation and Rearrangement of NH-Isoxazolines and Copper Catalyzed 6 Pi Electrocyclization","abstract":"Enaminones are a privileged motif that have both nucleophilic and electrophilic reactivity embedded within. Finding new ways to access these compounds is of high interest. The Anderson group is interested in utilizing [3,3] sigmatropic rearrangements to access new N-heterocycles in diastereoselective fashion. The work described in Chapter 1 features a new method for accessing enaminones utilizing a cascade approach that features an N–vinylisoxazoline intermediate that undergoes [3,3] sigmatropic rearrangement to form densely functionalized exocyclic vinylogous pyrrolidines. The functionalization of these compounds showcased a unique reactivity at the gem-dione under basic conditions and the mechanism of the corresponding products was further investigated. Chapter 2 discusses a ring expansion reaction of azetidine–N–oxides to form highly functionalized isoxazolidine products with up to 3 contiguous stereocenters in excellent diastereoselectivity. The scope was explored and shown to be tolerant for a wide array of aniline nucleophiles as well as a limited number of amines and alcohols with various azetidine–N–oxides. Chapter 3 is centered around establishing a method for copper catalyzed 6 π electrocyclization to form morpholines and morpholine–N–oxides via an initial Chan–Lam coupling followed by spontaneous electrocyclization.","abstract_html":"Enaminones are a privileged motif that have both nucleophilic and electrophilic reactivity embedded within. Finding new ways to access these compounds is of high interest. The Anderson group is interested in utilizing [3,3] sigmatropic rearrangements to access new N-heterocycles in diastereoselective fashion. The work described in Chapter 1 features a new method for accessing enaminones utilizing a cascade approach that features an N–vinylisoxazoline intermediate that undergoes [3,3] sigmatropic rearrangement to form densely functionalized exocyclic vinylogous pyrrolidines. The functionalization of these compounds showcased a unique reactivity at the gem-dione under basic conditions and the mechanism of the corresponding products was further investigated. Chapter 2 discusses a ring expansion reaction of azetidine–N–oxides to form highly functionalized isoxazolidine products with up to 3 contiguous stereocenters in excellent diastereoselectivity. The scope was explored and shown to be tolerant for a wide array of aniline nucleophiles as well as a limited number of amines and alcohols with various azetidine–N–oxides. Chapter 3 is centered around establishing a method for copper catalyzed 6 π electrocyclization to form morpholines and morpholine–N–oxides via an initial Chan–Lam coupling followed by spontaneous electrocyclization.","abstract_has_math":false,"creators":["Dylan Cole Keane (24399965)"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2026,"date_issued":"2026-05-01T00:00:00Z","date_published":"2026-05-01T00:00:00Z","updated_at":"2026-07-27T21:33:46Z","subjects":["Methodology"],"languages":[],"rights":["In Copyright","Open Access after 2028-05-01"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://doi.org/10.25417/uic.32994977.v1","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Dylan Cole Keane (24399965)"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2026-05-01T00:00:00Z"]},{"key":"dc:relation","label":"Dc Relation","values":["https://figshare.com/articles/thesis/Synthesis_Vinylation_and_Rearrangement_of_NH-Isoxazolines_and_Copper_Catalyzed_6_Pi_Electrocyclization/32994977"]},{"key":"dc:type","label":"Dc Type","values":["Text","Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Methodology"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright","Open Access after 2028-05-01"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["10.25417/uic.32994977.v1"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Enaminones are a privileged motif that have both nucleophilic and electrophilic reactivity embedded within. Finding new ways to access these compounds is of high interest. The Anderson group is interested in utilizing [3,3] sigmatropic rearrangements to access new N-heterocycles in diastereoselective fashion. The work described in Chapter 1 features a new method for accessing enaminones utilizing a cascade approach that features an N–vinylisoxazoline intermediate that undergoes [3,3] sigmatropic rearrangement to form densely functionalized exocyclic vinylogous pyrrolidines. The functionalization of these compounds showcased a unique reactivity at the gem-dione under basic conditions and the mechanism of the corresponding products was further investigated. Chapter 2 discusses a ring expansion reaction of azetidine–N–oxides to form highly functionalized isoxazolidine products with up to 3 contiguous stereocenters in excellent diastereoselectivity. The scope was explored and shown to be tolerant for a wide array of aniline nucleophiles as well as a limited number of amines and alcohols with various azetidine–N–oxides. Chapter 3 is centered around establishing a method for copper catalyzed 6 π electrocyclization to form morpholines and morpholine–N–oxides via an initial Chan–Lam coupling followed by spontaneous electrocyclization."]},{"key":"dc:title","label":"Title","values":["Synthesis, Vinylation and Rearrangement of NH-Isoxazolines and Copper Catalyzed 6 Pi Electrocyclization"]}]}],"canonical_facts":{"dc:creator":["Dylan Cole Keane (24399965)"],"dc:date":["2026-05-01T00:00:00Z"],"dc:description":["Enaminones are a privileged motif that have both nucleophilic and electrophilic reactivity embedded within. Finding new ways to access these compounds is of high interest. The Anderson group is interested in utilizing [3,3] sigmatropic rearrangements to access new N-heterocycles in diastereoselective fashion. The work described in Chapter 1 features a new method for accessing enaminones utilizing a cascade approach that features an N–vinylisoxazoline intermediate that undergoes [3,3] sigmatropic rearrangement to form densely functionalized exocyclic vinylogous pyrrolidines. The functionalization of these compounds showcased a unique reactivity at the gem-dione under basic conditions and the mechanism of the corresponding products was further investigated. Chapter 2 discusses a ring expansion reaction of azetidine–N–oxides to form highly functionalized isoxazolidine products with up to 3 contiguous stereocenters in excellent diastereoselectivity. The scope was explored and shown to be tolerant for a wide array of aniline nucleophiles as well as a limited number of amines and alcohols with various azetidine–N–oxides. Chapter 3 is centered around establishing a method for copper catalyzed 6 π electrocyclization to form morpholines and morpholine–N–oxides via an initial Chan–Lam coupling followed by spontaneous electrocyclization."],"dc:identifier":["10.25417/uic.32994977.v1"],"dc:relation":["https://figshare.com/articles/thesis/Synthesis_Vinylation_and_Rearrangement_of_NH-Isoxazolines_and_Copper_Catalyzed_6_Pi_Electrocyclization/32994977"],"dc:rights":["In Copyright","Open Access after 2028-05-01"],"dc:subject":["Methodology"],"dc:title":["Synthesis, Vinylation and Rearrangement of NH-Isoxazolines and Copper Catalyzed 6 Pi Electrocyclization"],"dc:type":["Text","Thesis"]},"updated_at":"2026-07-27T21:33:46Z"}