西松烯内酯的全合成研究 Ⅰ.关键中间体(2E,8E,12E)-3,9,13-三甲基-6-(1′-甲基乙烯基)-2,8,12-十四碳三烯-7-羟基-苯基砜的合成

Studies on the Total Synthesis of Cembranolide Ⅰ.Synthesis of the Key Intermediate(2E,8E,12E)-3,9,13-trimethyl-6-isopropenyl-2,8,12-tetradecatrien7-hydroxy-phenylsulfone

应用改进的合成砜的方法以获得烯丙基砜,再经二氧化硒和叔丁基过氧化氢氧化并与三溴化磷作用,生成ω-溴代砜,后者在低价铬的作用下与柠檬醛缩合便获得西松烯内酯的一个关键中间体(2E,8E,12E)-3,9,13-三甲基-6(1′甲基乙烯基)-2,8,12-十四碳三烯-7-羟基-苯基砜。

An improved sulfonation method was employed to obtain the allylic sulfone and then it was oxidized by selenium dioxide and t-butyl hydroperoxide.The product was treated with PBr_3 to afford ω-bromo sulfone,which was then condensed with citral by Hiyama′s method to give the key intermediate(2E,8E,12E)-3,9,13-trimethyl-6-isproenyl-2,8,12-tetradecatrien-7-hydroxy-phenylsulfone.