{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/98785"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/98785","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Chiral phosphine-catalyzed asymmetric transformations of allenoates and alkynoates and photoinduced, copper-catalyzed C-N couplings with aromatic nitrogen ceterocycles","abstract":"Chapter 1 describes the development of chiral biphenyl-derived phosphepines and their application as catalysts for an asymmetric [4 + 1] annulation to form functionalized cyclopentenes bearing a non-spirocyclic quaternary stereocenter. Additional studies demonstrate the synthetic utility of the cyclopentene products for further stereoselective functionalization and provide insight into the mechanism of the reaction. Chapter 2 describes the development of photoinduced, copper-catalyzed C-N couplings between aromatic nitrogen heterocycles (i.e., indole, benzimidazole, imidazole, and carbazole) and aryl, alkenyl, and alkynyl halides. These reactions utilize an inexpensive catalyst (Cul, without an additional ligand) and proceed at unusually low temperature for Ullmann coupling processes with these heterocycles (room temperature). Additional studies probe the selectivity of the reaction with respect to both the nucleophilic and the electrophilic coupling partner. Chapter 3 details progress towards developing a method for asymmetric, intermolecular y additions of oxygen nucleophiles to alkynoates using a chiral phosphine catalyst. Conditions are presented that effectively couple alkynoates bearing an aryl substituent at the y position with a variety of alcohols in good yield and high ee. Future efforts will be focused on expanding the scope of this process and conducting experiments to gain insight into the reaction mechanism.","abstract_html":"Chapter 1 describes the development of chiral biphenyl-derived phosphepines and their application as catalysts for an asymmetric [4 + 1] annulation to form functionalized cyclopentenes bearing a non-spirocyclic quaternary stereocenter. Additional studies demonstrate the synthetic utility of the cyclopentene products for further stereoselective functionalization and provide insight into the mechanism of the reaction. Chapter 2 describes the development of photoinduced, copper-catalyzed C-N couplings between aromatic nitrogen heterocycles (i.e., indole, benzimidazole, imidazole, and carbazole) and aryl, alkenyl, and alkynyl halides. These reactions utilize an inexpensive catalyst (Cul, without an additional ligand) and proceed at unusually low temperature for Ullmann coupling processes with these heterocycles (room temperature). Additional studies probe the selectivity of the reaction with respect to both the nucleophilic and the electrophilic coupling partner. Chapter 3 details progress towards developing a method for asymmetric, intermolecular y additions of oxygen nucleophiles to alkynoates using a chiral phosphine catalyst. Conditions are presented that effectively couple alkynoates bearing an aryl substituent at the y position with a variety of alcohols in good yield and high ee. Future efforts will be focused on expanding the scope of this process and conducting experiments to gain insight into the reaction mechanism.","abstract_has_math":false,"creators":["Ziegler, Daniel Todd"],"institution":"Massachusetts Institute of Technology","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry.","school":null,"contributors":[],"advisors":["Gregory C. Fu."],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015","date_published":"2015","updated_at":"2026-07-22T22:22:22Z","subjects":["Chemistry."],"languages":["eng"],"rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"rights_urls":["http://dspace.mit.edu/handle/1721.1/7582"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1721.1/98785","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Gregory C. Fu."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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Department of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Ziegler, Daniel Todd"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2015-09-17T19:11:56Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2015-09-17T19:11:56Z"]},{"key":"dc:date.issued","label":"Date","values":["2015"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://dspace.mit.edu/handle/1721.1/7582"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1721.1/98785"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2015.","Vita. Cataloged from PDF version of thesis.","Includes bibliographical references."]},{"key":"dc:description.abstract","label":"Abstract","values":["Chapter 1 describes the development of chiral biphenyl-derived phosphepines and their application as catalysts for an asymmetric [4 + 1] annulation to form functionalized cyclopentenes bearing a non-spirocyclic quaternary stereocenter. Additional studies demonstrate the synthetic utility of the cyclopentene products for further stereoselective functionalization and provide insight into the mechanism of the reaction. Chapter 2 describes the development of photoinduced, copper-catalyzed C-N couplings between aromatic nitrogen heterocycles (i.e., indole, benzimidazole, imidazole, and carbazole) and aryl, alkenyl, and alkynyl halides. These reactions utilize an inexpensive catalyst (Cul, without an additional ligand) and proceed at unusually low temperature for Ullmann coupling processes with these heterocycles (room temperature). Additional studies probe the selectivity of the reaction with respect to both the nucleophilic and the electrophilic coupling partner. Chapter 3 details progress towards developing a method for asymmetric, intermolecular y additions of oxygen nucleophiles to alkynoates using a chiral phosphine catalyst. Conditions are presented that effectively couple alkynoates bearing an aryl substituent at the y position with a variety of alcohols in good yield and high ee. Future efforts will be focused on expanding the scope of this process and conducting experiments to gain insight into the reaction mechanism."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D. in Organic Chemistry"]},{"key":"dc:title","label":"Title","values":["Chiral phosphine-catalyzed asymmetric transformations of allenoates and alkynoates and photoinduced, copper-catalyzed C-N couplings with aromatic nitrogen ceterocycles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Gregory C. Fu."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. Department of Chemistry."],"dc:creator":["Ziegler, Daniel Todd"],"dc:date.accessioned":["2015-09-17T19:11:56Z"],"dc:date.available":["2015-09-17T19:11:56Z"],"dc:date.issued":["2015"],"dc:description":["Thesis: Ph. D. in Organic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2015.","Vita. Cataloged from PDF version of thesis.","Includes bibliographical references."],"dc:description.abstract":["Chapter 1 describes the development of chiral biphenyl-derived phosphepines and their application as catalysts for an asymmetric [4 + 1] annulation to form functionalized cyclopentenes bearing a non-spirocyclic quaternary stereocenter. Additional studies demonstrate the synthetic utility of the cyclopentene products for further stereoselective functionalization and provide insight into the mechanism of the reaction. Chapter 2 describes the development of photoinduced, copper-catalyzed C-N couplings between aromatic nitrogen heterocycles (i.e., indole, benzimidazole, imidazole, and carbazole) and aryl, alkenyl, and alkynyl halides. These reactions utilize an inexpensive catalyst (Cul, without an additional ligand) and proceed at unusually low temperature for Ullmann coupling processes with these heterocycles (room temperature). Additional studies probe the selectivity of the reaction with respect to both the nucleophilic and the electrophilic coupling partner. Chapter 3 details progress towards developing a method for asymmetric, intermolecular y additions of oxygen nucleophiles to alkynoates using a chiral phosphine catalyst. Conditions are presented that effectively couple alkynoates bearing an aryl substituent at the y position with a variety of alcohols in good yield and high ee. Future efforts will be focused on expanding the scope of this process and conducting experiments to gain insight into the reaction mechanism."],"dc:description.degree":["Ph. D. in Organic Chemistry"],"dc:identifier.uri":["http://hdl.handle.net/1721.1/98785"],"dc:language.iso":["eng"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission."],"dc:rights.uri":["http://dspace.mit.edu/handle/1721.1/7582"],"dc:subject":["Chemistry."],"dc:title":["Chiral phosphine-catalyzed asymmetric transformations of allenoates and alkynoates and photoinduced, copper-catalyzed C-N couplings with aromatic nitrogen ceterocycles"],"dc:type":["Thesis"]},"updated_at":"2026-07-22T22:22:22Z"}