{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/68544"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/68544","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Enantioselective [4 + 2] cycloadditions of iminoacetonitriles : application to the total synthesis of (-)-quinolizidine 2071","abstract":"Iminoacetonitriles participate as reactive dienophiles in intramolecular Diels-Alder cycloadditions affording quinolizidines and indolizidines. The resulting a-amino nitrile cycloadducts are versatile intermediates that can be further elaborated in a stereoselective manner. This thesis describes the development of intramolecular, enantioselective aza Diels- Alder cycloadditions promoted by chiral Brønsted acids as well as the discovery that iminoacetonitriles can also participate in acid catalyzed cycloadditions. The second part of this thesis reports the total synthesis of (-)-quinolizidine 2071 using an intramolecular, enantioselective cycloaddition of an iminoacetonitrile as the key step.","abstract_html":"Iminoacetonitriles participate as reactive dienophiles in intramolecular Diels-Alder cycloadditions affording quinolizidines and indolizidines. The resulting a-amino nitrile cycloadducts are versatile intermediates that can be further elaborated in a stereoselective manner. This thesis describes the development of intramolecular, enantioselective aza Diels- Alder cycloadditions promoted by chiral Brønsted acids as well as the discovery that iminoacetonitriles can also participate in acid catalyzed cycloadditions. The second part of this thesis reports the total synthesis of (-)-quinolizidine 2071 using an intramolecular, enantioselective cycloaddition of an iminoacetonitrile as the key step.","abstract_has_math":false,"creators":["Fontaine, Shaun D. (Shaun David)"],"institution":"Massachusetts Institute of Technology","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Dept. of Chemistry.","school":null,"contributors":[],"advisors":["Rick L. Danheiser."],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011","date_published":"2011","updated_at":"2026-07-22T22:21:53Z","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/1721.1/68544","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Rick L. Danheiser."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:contributor.other","label":"Dc Contributor Other","values":["Massachusetts Institute of Technology. Dept. of Chemistry."]},{"key":"dc:creator","label":"Author","values":["Fontaine, Shaun D. 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This thesis describes the development of intramolecular, enantioselective aza Diels- Alder cycloadditions promoted by chiral Brønsted acids as well as the discovery that iminoacetonitriles can also participate in acid catalyzed cycloadditions. The second part of this thesis reports the total synthesis of (-)-quinolizidine 2071 using an intramolecular, enantioselective cycloaddition of an iminoacetonitrile as the key step."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Enantioselective [4 + 2] cycloadditions of iminoacetonitriles : application to the total synthesis of (-)-quinolizidine 2071"]}]}],"canonical_facts":{"dc:contributor.advisor":["Rick L. Danheiser."],"dc:contributor.department":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:contributor.other":["Massachusetts Institute of Technology. Dept. of Chemistry."],"dc:creator":["Fontaine, Shaun D. (Shaun David)"],"dc:date.accessioned":["2012-01-12T19:36:09Z"],"dc:date.available":["2012-01-12T19:36:09Z"],"dc:date.issued":["2011"],"dc:description":["Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011.","Vita. Cataloged from PDF version of thesis.","Includes bibliographical references."],"dc:description.abstract":["Iminoacetonitriles participate as reactive dienophiles in intramolecular Diels-Alder cycloadditions affording quinolizidines and indolizidines. The resulting a-amino nitrile cycloadducts are versatile intermediates that can be further elaborated in a stereoselective manner. This thesis describes the development of intramolecular, enantioselective aza Diels- Alder cycloadditions promoted by chiral Brønsted acids as well as the discovery that iminoacetonitriles can also participate in acid catalyzed cycloadditions. 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