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

 

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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.

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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.