Intramolecular [2+2+2] cycloaddition reactions of Yne-ene-yne and Yne-yne-ene enediynes catalysed by Rh I: Experimental and theoretical mechanistic studies

Anna Dachs, Anna Pla-Quintana, Teodor Parella, Miquel Solà, Anna Roglans

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    23 Citations (Scopus)

    Abstract

    N-Tosyl-linked open-chain yne-ene-yne enediynes 1 and 2 and yne-yne-ene enediynes 3 and 4 have been satisfactorily synthesised. The [2+2+2] cycloaddition process catalysed by the Wilkinson catalyst [RhCl(PPh 3) 3] was tested with the above-mentioned substrates resulting in the production of high yields of the cycloadducts. Enediynes 1 and 2 gave standard [2+2+2] cycloaddition reactions whereas enediynes 3 and 4 suffered β-hydride elimination followed by reductive elimination of the Wilkinson catalyst to give cycloadducts, which are isomers of those that would be obtained by standard [2+2+2] cycloaddition reactions. The different reactivities of these two types of enediyne have been rationalised by density functional theory calculations. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Original languageEnglish
    Pages (from-to)14493-14507
    JournalChemistry - A European Journal
    Volume17
    Issue number51
    DOIs
    Publication statusPublished - 16 Dec 2011

    Keywords

    • cycloaddition
    • density functional calculations
    • enediynes
    • reaction mechanisms
    • rhodium

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