Neighboring nucleophilic group assisted rearrangement of allylic esters under Eu(fod)3 catalysis

The acetate 13a and methoxyacetate 13b of (E)-3-hydroxy-4-(arylmethylidene)cyclodeca-1,5-diyne possessing a free hydroxy group underwent an allylic rearrangement at 20°C in the presence of catalytic Eu(fod)3 to give the enediyne 14 in excellent yields. In contrast, the acetate 10a with a silyloxy group failed to rearrange under the same conditions. These results demonstrated that an internal nucleophilic group promotes the Eu(fod)3-catalyzed rearrangement of allylic esters under mild conditions.