A pair of Mn^III(quinazolinone) complexes was prepared and evaluated in the catalytic epoxidation of the chiral allylic alcohols and unfunctionalised alkenes with iodosylbenzene. Epoxidation of chiral allylic alcohols with 1,3-allylic strain proceeded chemo- and diastereoselectively to give threo-epoxy alcohol (up to 99% d.r). Epoxidation of unfunctionalised alkenes by the proposed catalyst system proceeded nonselectively, as evidenced by the formation of isomerization and rearrangement products in the epoxidation of (Z)-stilbene. A three-step pathway involving a cationic intermediate is proposed for the formation of isomerization and rearrangement products. The fact that only products resulting from the cationic intermediate were detected in the oxidation of a mechanistic probe, (2-methoxy-3-vinylcyclopropyl)benzene, with Mn^III(quinazolinone) and PhIO substantiated the cationic oxygen transfer mechanism.

制备了一对Mn ^III（喹唑啉酮）配合物，并用碘代苯催化手性烯丙基醇和未官能化烯烃的环氧化反应。与1,3-手性烯丙基醇的环氧化-烯丙基应变进行化疗和非对映选择性得到苏式-环氧醇（高达99％的DR）。通过所提出的催化剂体系对未官能化的烯烃的环氧化非选择性地进行，这通过（Z）-二苯乙烯环氧化中异构化和重排产物的形成来证明。一个三-为形成异构化和重排产物，提出了一种涉及阳离子中间体的步骤。在机械探针（2-甲氧基-3-乙烯基环丙基）苯与Mn ^III（喹唑啉酮）和PhIO的氧化中仅检测到由阳离子中间体产生的产物这一事实证实了阳离子氧的转移机理。