Reactions of a stable (phosphanyl)(silyl)carbene with aliphatic aldehydes: [2+1] versus [2+2] addition to a carbonyl group

Ona Illa, Heinz Gornitzka, Vicenç Branchadell, Antoine Baceiredo, Guy Bertrand, Rosa M. Ortuño

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The reactions between the stable (phosphanyl)(silyl)carbene 1 and different aliphatic aldehydes have been investigated for the first time. Results reveal that two competitive processes take place. The kinetically most favorable one is a concerted [2+1] cycloaddition to carbonyl leading to oxiranes as single diastereomers, with the trans arrangement of the alkyl and phosphoranyl groups, as the major products. Simultaneously, a [2+2]-like addition provides short-lived oxaphosphetene intermediates that rapidly evolve to the corresponding olefins with E stereochemistry, which are the thermodynamically most stable compounds. DFT calculations establish the mechanism for both processes and a rationale for the observed diastereoselectivity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
Original languageEnglish
Pages (from-to)3147-3152
JournalEuropean Journal of Organic Chemistry
Issue number16
Publication statusPublished - 11 Aug 2003


  • Carbenes
  • Cycloadditions
  • Oxiranes
  • Phosphorus


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