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Rick L. Danheiser. Amos, David Thomas, 1975- Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2006-03-24T18:12:04Z 2006-03-24T18:12:04Z 2003 2003 http://hdl.handle.net/1721.1/30015 55025081 Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003. Vita. Includes bibliographical references. Iminoacetonitriles have been shown to function as aza dienophiles in intramolecular Diels-Alder reactions, affording substituted quinolizidines and indolizidines. The cycloadducts are formed with a high preference for an exo-orientated cyano group due to the a-amino nitrile anomeric effect. The substrates for these [4+2] cycloadditions are prepared from readily available alcohols via a Mitsunobu reaction with the previously unknown N-cyanomethyltriflamide (HN(Tf)CH₂CN) followed by cesium carbonate promoted elimination of trifluoromethanesulfinate. The a-amino nitrile cycloadducts are versatile synthetic intermediates and can be elaborated via alkylation, reduction, and nucleophilic addition chemistry to provide a variety of substituted and functionalized nitrogen heterocycles. Initial investigations have been undertaken to explore the use of this methodology in the total synthesis of alkaloid natural products. by David Thomas Amos. Ph.D. 367 p. 9370189 bytes 9369989 bytes application/pdf application/pdf eng Massachusetts Institute of Technology 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. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Synthesis of nitrogen heterocycles via the intramolecular [4+2] cycloaddition of iminoacetonitriles Thesis application/pdf Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="be0b941a-e7d8-41c6-bd49-6560560572a9"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Synthesis of nitrogen heterocycles via the intramolecular [4+2] cycloaddition of iminoacetonitriles</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2003</PublicationDate> <Authors> <Author> <DisplayName>Amos, David Thomas, 1975-</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>Iminoacetonitriles have been shown to function as aza dienophiles in intramolecular Diels-Alder reactions, affording substituted quinolizidines and indolizidines. The cycloadducts are formed with a high preference for an exo-orientated cyano group due to the a-amino nitrile anomeric effect. The substrates for these [4+2] cycloadditions are prepared from readily available alcohols via a Mitsunobu reaction with the previously unknown N-cyanomethyltriflamide (HN(Tf)CH₂CN) followed by cesium carbonate promoted elimination of trifluoromethanesulfinate. The a-amino nitrile cycloadducts are versatile synthetic intermediates and can be elaborated via alkylation, reduction, and nucleophilic addition chemistry to provide a variety of substituted and functionalized nitrogen heterocycles. Initial investigations have been undertaken to explore the use of this methodology in the total synthesis of alkaloid natural products.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>