The development of iterative and cascade methods for the rapid synthesis of ladder polyether natural products
Name
61772167-MIT.pdf
Description
Full printable version
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Author(s)
Heffron, Timothy Paul
Advisor(s)
Timothy F. Jamison.
Date Issued
2005
Publisher
Massachusetts Institute of Technology
Abstract
I. The Development of Methods for the Iterative Synthesis of Polytetrahydropyrans An iterative method comprising chain homologation, epoxidation, 6-endo cyclization, and protiodesilylation was developed. Notable achievements include the development of a novel propargyl organocopper coupling method, and the complete control of stereoselectivity and regioselectivity during the iterative synthesis of a tristetrahydropyran. The synthesis of the tristetrahydropyran was achieved in 18 total operations. ... (1) homologation (2) epoxidation (3) cyclization (4) protiodesilylation ... II. The Development of a Cascade Synthesis of Polytetrahydropyrans with No Directing Groups at Ring Junctions Cascade approaches to trans-fused tetrahydropyrans were studied. After exploring acid-promoted cascade cyclizations of polyepoxysilanes and polyepoxides without directing groups, the base-promoted cascade cyclization of polyepoxysilanes was realized. In this method, as many as five operations take place in a single step to provide a tristetrahydropyran with no directing groups at any ring junctions. The synthesis of the tristetrahydropyran was accomplished in 11 steps. ...
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005.
MIT Science Library copy: Issued in leaves, in a 2 v. set.
Also issued in leaves, in a 2 v. set. Vita.
Includes bibliographical references .
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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