A novel PhI(OAc)₂-mediated dialkoxylation of 4-aminostyrenes has been developed. A range of 2,3-disubstituted 1,4-dioxane or 1,2-dimethoxyethane derivatives were formed in 15 to 95% yields with high diastereoselectivities. This transformation was distinct from the previously reported hypervalent iodine(III)-mediated dioxygenation reaction, a process via the formation of a cyclic iodonium ion intermediate. This protocol involves an oxidative dearomatization-induced nucleophilic attack and an aromatization-induced 1,6-conjugated addition.

中文翻译：

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PhI（OAc）₂在无金属条件下通过脱芳香化过程介导的4-氨基苯乙烯的二烷氧基化反应

已经开发了新颖的PhI（OAc）₂介导的4-氨基苯乙烯的二烷氧基化。以高非对映选择性以15％至95％的收率形成了一系列2,3-二取代的1,4-二恶烷或1,2-二甲氧基乙烷衍生物。该转变不同于先前报道的高价碘（III）介导的双加氧反应，该反应是通过形成环状碘鎓离子中间体而形成的。该协议涉及氧化脱芳香化诱导的亲核攻击和芳构化诱导的1，6-共轭加成。