Dirhodium(II) caprolactamate: An exceptional catalyst for allylic oxidation
Dirhodium(II) caprolactamate: An exceptional catalyst for allylic oxidation
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DOI：
10.1021/ja045330o
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发表时间：
2004-10-27
影响因子：
15
通讯作者：
Doyle, MP
中科院分区：
文献类型：
--
作者：
Catino, AJ;Forslund, RE;Doyle, MP
有机分子的氧化是一个非常重要的化学过程。特别重要的是烯丙基氧化，其中单个亚甲基单元直接转化为羰基。在这篇文章中，我们报道了己内酰胺二铑（II）[Rh 2（cap）4]与叔丁基过氧化氢（末端氧化剂）的组合有效地催化了各种烯烃和烯酮的烯丙基氧化。该反应是完全选择性的，耐受空气/水分，并且可以在几分钟内用低至0.1摩尔%的催化剂进行。提出了一种涉及氧化还原链催化的机理建议，以及高价dirhodiumtert-butyl过氧络合物的中间性的证据。
The oxidation of organic molecules represents a fundamentally important chemical process. Particularly important is allylic oxidation, whereby a single methylene unit is converted directly into a carbonyl group. In this communication, we report that dirhodium(II) caprolactamate [Rh2(cap)4] in combination withtert-butyl hydroperoxide (terminal oxidant) effectively catalyzes the allylic oxidation of a variety of olefins and enones. The reaction is completely selective, tolerant of air/moisture, and can be performed with as little as 0.1 mol % catalyst in minutes. A mechanistic proposal involving redox chain catalysis has been put forth, as well as evidence for the intermediacy of a higher valent dirhodiumtert-butyl peroxy complex.