Recent developments in the metal-catalyzed reactions of metallocarbenoids from propargylic esters.

The transition-metal-catalyzed intramolecular cycloisomerization of propargylic carboxylates provides functionalized bicyclo[n.1.0]enol esters in a very diastereoselective manner and, depending on the structure, with partial or complete transfer of chirality from enantiomerically pure precursors. The subsequent methanolysis gives bicyclo[n.1.0] ketones, hence resulting in a very efficient two-step protocol for the syntheses of alpha,beta-unsaturated cyclopropyl ketones, key intermediates for the preparation of natural products. The results from mechanistic computational studies suggest that they probably proceed through cyclopropyl metallocarbenoids, formed by endo-cyclopropanation, that undergo a 1,2-acyl migration. Finally, the potential of the intermolecular reaction and the related pentannulation of propargylic esters bearing pendant aromatic rings are also discussed.