Use of metal complexation in the synthesis of medium-ring acetylenic lactones

Abstract The hexacarbonyldicobalt complexes of several appropriately designed acetylenic lactone precursors have been prepared, and lactones containing Co 2 (CO) 6 -complexed triple bonds in seven-, ten-, and eleven-membered rings obtained. The latter were best obtained through a retro-Dieckmann fragmentation of 2-(hydroxybutynyl) derivatives of 1,3-clohexanedione. Attempts to extend this reaction to cyclohexanones bearing other anion-stabilizing groups in the 2-position or to 1,3-cyclopentanediones were unsuccessful. Decomplexation afforded the metal-free 11-ring lactone, characterized crystallographically. Treatment of this system with basic reagents led to dimerization. In the case of the smaller rings, cyclization of the complexed acetylenic hydroxyacids under Mukaiyama conditions (2-chloro- N -methylpyridinium iodide, CH 2 Cl 2 , reflux) succeeded in modest yields.