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  • Title: Transannular [4 + 2] Cycloaddition Reactions of Cobalt-Complexed Macrocyclic Dienynes.
    Author: Karabiyikoglu S, Merlic CA.
    Journal: Org Lett; 2015 Aug 21; 17(16):4086-9. PubMed ID: 26240955.
    Abstract:
    The first transannular [4 + 2] cycloaddition reactions of macrocyclic dicobalt hexacarbonyl-dienyne complexes were demonstrated. Complexes were conveniently prepared through palladium(II)-catalyzed intramolecular oxidative cyclization of bis(vinylboronate esters) followed by complexation with dicobalt octacarbonyl. Transannular [4 + 2] cycloaddition reactions of the complexes occurred at lower temperatures and shorter times than transannular Diels-Alder reactions of metal-free dienynes. Intermolecular control reactions confirmed the effect of cobalt complexation on [4 + 2] cycloaddition reactions of unactivated alkynes and dienes.
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