Synthesis of nitrogen heterocycles via the intramolecular [4+2] cycloaddition of iminoacetonitriles
Name
55025081-MIT.pdf
Description
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8.94 MB
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Checksum (MD5)
cde3e13302eecb52cee1269465079c59
Author(s)
Amos, David Thomas, 1975-
Advisor(s)
Rick L. Danheiser.
Date Issued
2003
Publisher
Massachusetts Institute of Technology
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.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.
Vita.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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