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

The acetate 13a and methoxyacelate 13b of (E)-3-hydroxy-4-(arylmethylidene) cyclodeca-1,5-diyne possessing a free hydroxy group underwent an allylic re arrangement at 20 degreesC in the presence of catalytic Eu(fod)(3) to give the enediyne 14 in excellent yields. In contrast, the acetate 10a with a si lyloxy group failed to rearrange under the same conditions. These results d emonstrated that an internal nucleophilic group promotes the Eu(fod)(3)-cat alyzed rearrangement of allylic eaters under mild conditions. (C) 2001 Else vier Science Ltd. All rights reserved.