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Synlett 2008(5): 751-754  
DOI: 10.1055/s-2008-1032113
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© Georg Thieme Verlag Stuttgart · New York

Thermal Intramolecular Alder-Ene Cycloisomerization of 1,6-Allenynes

Olivier Buisine, Vincent Gandon, Louis Fensterbank, Corinne Aubert*, Max Malacria*
Laboratoire de Chimie Organique UMR 7611, Institut de Chimie Moléculaire FR2769, Université Pierre et Marie Curie-Paris 6, Tour 44-54, 4 Place Jussieu 75252 Paris, France
Fax: +33(1)44277360; e-Mail: max.malacria@upmc.fr;
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Publication History

Received 28 November 2007
Publication Date:
26 February 2008 (online)

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Abstract

Alder-ene cycloisomerizations of 1,6-allenynes occur without catalysts under refluxing conditions. Depending on the substrate, THF, toluene, or xylenes can be used as solvents to provide the corresponding 6-methylene-1-vinylcyclohexene in up to 98% yield.

Key words - allenes - alkynes - cyclizations - ene reactions - trienes

    References and Notes

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3

The configuration of 5b, as well as 5c,f,g,i (see Table [1] ), was ascertained by NOE experiment between the vinyl proton at R4 and the R3 substituent.

6

The vinyl carbanionic fragment in compounds of type C can be cis or trans. The isomer depicted in Scheme [3] was found to be formed preferably in all cases by ca 2 kcal/mol of enthalpy of activation.