Tandem PtCl2 catalyzed–thermal [3,3] rearrangements of enyne acetates

1,6 Enyne systems flanked with an acetate group at the propargyl position undergo tandem PtCl2-catalyzed–thermal [3,3] rearrangements leading to trienes. The scope of the transformation has been delineated by varying the nature of the alkynyl substituent R. For R=alkyl or phenyl, a direct 1,3-migration of the acetate group is proposed leading to an allenyl ester intermediate that undergoes a subsequent [3,3] rearrangement.