Halonium Ion-Mediated Reaction of Unsaturated Hydroperoxy Acetals. Competition between the Formation of Cyclic Peroxides and the Migration of the Methoxy (or Hydroxy) Group
作者:Takahiro Tokuyasu、Araki Masuyama、Masatomo Nojima、Kevin J. McCullough
DOI:10.1021/jo991499m
日期:2000.2.1
Monoozonolyses of dienes 2 in methanol gave in each case the corresponding unsaturated alpha-methoxy hydroperoxides 3. Capture of 2-alkyl-substituted cyclohexanone oxides by methanol was highly diastereoselective, thereby providing exclusively the hydroperoxides derived from attack by methanol from the less hindered face of the carbonyl oxide intermediates. Halonium ion-mediated reactions of the hydroperoxides
二烯2在甲醇中的单臭氧分解反应分别得到相应的不饱和α-甲氧基氢过氧化物3。甲醇对2-烷基取代的环己酮氧化物的捕获具有极高的非对映选择性,从而仅从受阻较弱的表面提供了甲醇侵蚀产生的氢过氧化物。羰基氧化物中间体。氢离子过氧化氢3的卤离子介导反应产生了新的甲氧基或羟基迁移产物,以及预期的卤素取代的1,2-二恶烷和/或1,2-二氧杂戊环酮,产物混合物的组成取决于所使用的卤化剂的种类和结构3。