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  • 1
    ISSN: 1434-193X
    Keywords: Rearrangements ; Density functional calculations ; Substituent effects ; Transition structures ; Small-ring compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Two possible types of competing [1,3] rearrangements of divinylcyclopropane derivatives and of the hetero-analogous compounds vinylcyclopropanecarbaldehyde and vinylcyclopropanecarbthioaldehyde to five-membered ring compounds have been investigated theoretically by (U)DFT (Becke3LYP/6-31G*) methodology. Although both of the rearrangement pathways correspond to a reaction of the monosubstituted cyclopropane substructure, i.e. a reaction of vinylcyclopropane or of cyclopropanecarb(thio)aldehyde, new features in the reactivity are seen due to the combination of two substituents. Reaction parameters such as reaction and activation energies of the [1,3]-sigmatropic rearrangements have been calculated and compared. Substituent effects of hydroxy and formyl (donor and acceptor) groups in specific positions have also been considered. On the basis of these calculations, the [1,3] rearrangement of vinylcyclopropanecarbaldehydes to dihydrofurans can be expected to be kinetically favored over their conversion to cyclopentenes, while formation of the latter should be favored thermodynamically. This prediction is borne out by the experimental findings. Depending on the substitution pattern, the [1,3]-sigmatropic rearrangement of vinylcyclopropanecarbaldehydes may compete with the [3,3]-sigmatropic rearrangement. For the other investigated structures, the [1,3] rearrangement is strongly disfavored.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/98456_s.pdf or from the author.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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