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Gold-Catalyzed 1,3-Acyloxy Migration/5-exo-dig Cyclization/1,5-Acyl Migration of Diynyl Esters


  • This work was supported by CNRS and ANR BLAN (06-2_159258). L.F. and M.M. are members of the IUF. We used the computing facilities of CRIHAN (project 2006-013). We thank K. Brummond for useful discussions.


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Working three shifts: Polyconjugated δ-diketones are formed stereoselectively in high yields by the gold-catalyzed rearrangement of 1,6-diyn-3-yl esters. This cascade involves a 1,3-sigmatropic acyloxy shift, a 5-exo-dig cyclization of the resulting allenyne, and an unprecedented 1,5-sigmatropic shift of an acyl fragment. The usefulness of the products was shown by an efficient acid-catalyzed transformation into a complex polycyclic framework.

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