Palladium-catalyzed intramolecular oxidative alkylation of 4-pentenyl beta-dicarbonyl compounds.


Journal Article

Reaction of 8-nonene-2,4-dione with a catalytic amount of [PdCl2(CH3CN)2] (2; 5 mol %) and a stoichiometric amount of CuCl2 (2.5 equiv) at room temperature for 3 h led to oxidative alkylation and formation of 2-acetyl-3-methyl-2-cyclohexenone in 80 % isolated yield. The oxidative alkylation of 4-pentenyl beta-diketones tolerated a number of terminal acyl groups and substitution at the C1 and C3 carbon atoms of the 4-pentenyl chain. Likewise, 4-pentenyl beta-keto esters that possessed geminal disubstitution at the C1, C2, or C3 carbon atom of the 4-pentenyl chain cyclized to form 2-carboalkoxy-2-cyclohexenones in moderate to good yield as the exclusive cyclized product. Deuterium-labeling experiments provided information regarding the mechanism of the palladium-catalyzed oxidative alkylation of 4-pentenyl beta-dicarbonyl compounds.

Full Text

Duke Authors

Cited Authors

  • Liu, C; Wang, X; Pei, T; Widenhoefer, RA

Published Date

  • December 2004

Published In

Volume / Issue

  • 10 / 24

Start / End Page

  • 6343 - 6352

PubMed ID

  • 15532056

Pubmed Central ID

  • 15532056

Electronic International Standard Serial Number (EISSN)

  • 1521-3765

International Standard Serial Number (ISSN)

  • 0947-6539

Digital Object Identifier (DOI)

  • 10.1002/chem.200400460


  • eng