University of Illinois Urbana-Champaign

Stereoselective Synthesis of Trisubstituted Olefins

Amburgey, Jack S.

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Description

Title
Stereoselective Synthesis of Trisubstituted Olefins
Author(s)
Amburgey, Jack S.
Issue Date
1994
Doctoral Committee Chair(s)
Denmark, Scott E.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Abstract
  • A new method for the highly stereoselective synthesis of trisubstituted olefins is presented. The method involves the stereoselective construction of various $\beta$-hydroxy phosphonamidates followed by their thermolysis to provide trisubstituted olefins in extremely high geometrical purity ($>$99/1).
  • The stereoselective construction of $\beta$-hydroxy phosphonamidates could be accomplished through three main synthetic transformations. The first involves the acylation of various parent 1,3,2-oxazaphospholidines to provide monoalkylated $\beta$-keto phosphonamidates in good yield. The second step is the alkylation of the $\beta$-keto phosphonamidates to provide $\alpha,\alpha$-dialkylated $\beta$-keto phosphonamidates in high yield and very high diastereoselectivities. Finally, the highly diastereoselective reduction of the dialkylated $\beta$-keto phosphonamidates could be accomplished through the use of a variety of reducing agents to give $\beta$-hydroxy phosphonamidates in high yield and high diastereoselectivities.
  • Thermolysis of the diastereomerically pure $\beta$-hydroxy phosphonamidates gave a variety of trisubstituted olefins in high yield and very high stereoselectivity. A discussion on anionic mediated olefinations as well as an extension into the stereoselective synthesis of tetrasubstituted olefins is also presented.
Graduation Semester
1994
Type of Resource
text
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http://hdl.handle.net/2142/72294

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