Synthesis of pyridines via [4 + 2] cycloadditions of vinylallenes with azadienophiles
Name
940564717-MIT.pdf
Description
Full printable version
Size
17.5 MB
Format
Adobe PDF
Checksum (MD5)
e4f1dc5a107adc357ab9657834c1809e
Author(s)
Hamzik, Philip J. (Philip Jonathan)
Date Issued
2015
Publisher
Massachusetts Institute of Technology
Abstract
Pyridines are an important class of heterocycle with widespread applications. However, the efficient preparation of substituted pyridines remains a challenge in organic synthesis. This thesis describes new annulation strategies for the synthesis of highly substituted pyridines that involve [4 + 2] cycloadditions of vinylallenes with azadienophiles. Part II of this thesis describes a unimolecular, formal [2 + 2 + 2] cycloaddition strategy for the synthesis of tricyclic pyridines based on intramolecular propargylic ene/imino Diels-Alder reaction cascades. In this variant, unactivated oximino ethers and NN-dialkylhydrazones function as dienophiles in thermal Diels-Alder reactions. Part III of this thesis describes strategies for the synthesis of bicyclic and monocyclic 2-sulfonylpyrdines based on [4 + 2] cycloadditions of vinylallenes with tosyl cyanide. In addition, Part III discusses the synthetic elaboration of these 2- sulfonylpyridines via nucleophilic aromatic substitution reactions. Overall, annulation strategies based on [4 + 2] cycloadditions of vinylallenes with azadienophiles have been developed for the preparation of highly substituted pyridines in an efficient, convergent, and regioselective fashion.
Description
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2015.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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