University of Illinois Urbana-Champaign

Broad-Spectrum Synthesis of Enantiomerically Pure Lactones

Adams, Paul Ernest

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Description

Title
Broad-Spectrum Synthesis of Enantiomerically Pure Lactones
Author(s)
Adams, Paul Ernest
Issue Date
1980
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
Language
eng
Abstract
  • A general synthetic approach that affords both enantiomers of chiral lactones is described. The key step involves the automated multigram chromatography of diastereomeric derivatives of a racemic intermediate. The generality of the method is demonstrated by the synthesis of ring-saturated lactones of three different ring sizes, a series of bicyclic lactones, (alpha), (beta)-unsaturated lactones, and several examples containing aromatic substituents. Six of these examples occur in nature as pheromones or allomones, and hence are of biological interest. Assignments of absolute configuration to the lactone enantiomers and their precursors typically attend these syntheses. For some lactones, possessing suitable NMR spectra, direct determination of enantiomeric purity is possible using the chiral solvent (R)-(-)-2, 2, 2-trifluoro-1-(9-anthryl) ethanol.
  • The 1, 4-conjugate addition of organometallic reagents to chiral (alpha), (beta)-unsaturated lactones has been found to proceed with a very high degree of stereospecificity. This reaction, when coupled with the lactone resolution, affords a straightforward sequence for the introduction of chiral centers remote from functionality in high enantiomeric purity.
Graduation Semester
1980
Type of Resource
text
Permalink
http://hdl.handle.net/2142/67218

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