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Synthesis 2010(8): 1321-1324  
DOI: 10.1055/s-0029-1219278
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Cobalt-Catalyzed Generation of 1,4-Dienes as Synthons for 1,3-Dicarbonyl Compounds and Their Application in Natural Product Syntheses

Gerhard Hilt*, Marion Arndt, Damian F. Weske
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany
Fax: +49(6421)2825677; e-Mail: Hilt@chemie.uni-marburg.de;
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Publikationsverlauf

Received 18 December 2009
Publikationsdatum:
25. Januar 2010 (online)

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Abstract

The cobalt-catalyzed 1,4-hydrovinylation of alkenes with 1,3-dienes and the cobalt-catalyzed Diels-Alder reaction of alkynes with 1,3-dienes lead to acyclic and cyclic 1,4-dienes, respectively. These products can be transformed into 1,3-dicarbonyl functional groups by ozonolysis or alternative carbon-carbon double bond cleaving reactions. The application towards the synthesis of hepialone and a pyranone-type lipid from Vanilla beans is described.

Key words

cobalt - cycloaddition - 1,3-dicarbonyl compounds - ­Diels-Alder - hydrovinylation - ozonolysis

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7

Ligands such as 2,4,6-trimethyl-N-(pyridin-2-ylmethyl-ene)aniline (as a representative of a pyridine-imine-type ligand) as well as N,N"-dibutylethane-1,2-diimine or N,N"-dicyclohexylethane-1,2-diimine (diimine-type ligands) can be applied.