Abstract
Treatment of 3-oxo-6-heptenoate esters 1, 2, 4-15 with 4 equiv of Mn(0Ac)3-2H20 and 1 equiv of Cu(0Ac)2-H20 gave salicylate esters 16-29 in yields of 17-78%. Similar treatment with 4 equiv of Mn(0Ac)3-2H20 and excess LiCl gave mixtures of salicylate esters and chlorides such as 45 and 46, which could be converted to the salicylate ester by heating at reflux in acetic acid containing excess LiCl in overall yields of 40-90%. Treatment of a-chloro /3-keto ester 3 with 2 equiv of Mn(0Ac)3-2H20 and 1 equiv of Cu(0Ac)2-H20 gave a mixture of salicylate 17 and methylenecyclohexane 41. Treatment of 5-hydroxy /3-keto esters 51a and 51b with 2 equiv of Mn(0Ac)3-2H20 gave epoxides 53a and 53b in 50% and 30% yield, respectively.