Synthesis of nitrogen heterocycles via the intramolecular [4+2] cycloaddition of iminoacetonitriles
Author(s)
Amos, David Thomas, 1975-
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Massachusetts Institute of Technology. Dept. of Chemistry.
Advisor
Rick L. Danheiser.
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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.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003. Vita. Includes bibliographical references.
Date issued
2003Department
Massachusetts Institute of Technology. Department of ChemistryPublisher
Massachusetts Institute of Technology
Keywords
Chemistry.