A silver-catalyzed intramolecular amidation of saturated C-H bonds
A silver-catalyzed intramolecular amidation of saturated C-H bonds
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DOI：
10.1002/anie.200454243
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
He, C
中科院分区：
文献类型：
--
作者：
Cui, Y;He, C
在过渡金属催化下，氧化插入反应成饱和CÀH键形成胺和胺衍生物是很有吸引力的合成方法。[1-14]这些反应除了可以方便地接触到各种有机结构外，还为研究CÀH活化的基本机制提供了机会。已经证明，铑和钌基化合物介导CÀH酰胺化反应特别好。[2,4,14 - 19]四羧酸二钠体系催化氨基甲酸酯和氨基甲酸酯CÀH键的分子内酰胺化，具有较高的区域选择性和良好的非对映选择性。[14-16]有人认为，在这些反应中可能会形成一种金属结合的亚硝基，然后以氧化的方式插入饱和的CÀH键中。尽管对CÀH键的金属催化酰胺化进行了广泛的研究，但这种过程的有效和实际例子有限。本文报道了一种由银(i)催化的饱和CÀH键的有效酰胺化反应。银配合物表现出有趣的活性，近年来银催化的有机转化引起了人们的关注。[20-23]特别是发现了几种由银催化的非自由基氧化基团转移反应。[24-27]我们报道了一种能有效催化烯烃叠氮化的化合物（1，方案1a）令人惊讶的是，随后的研究表明，只有这种蒸馏物
Oxidative insertion reactions into saturated CÀH bonds to form amines and amine derivatives under transition-metal catalysis are attractive synthetic methodologies.[1–14] Besides providing facile access to various organic structures, these reactions also offer opportunities to study the fundamental mechanism of CÀH activation. It has been demonstrated that Rh-and Ru-based compounds mediate CÀH amidation reactions particularly well.[2, 4, 14–19] A dirhodium (ii) tetracarboxylate system was shown to catalyze the intramolecular amidation of CÀH bonds of carbamates and sulfamates with high regioselectivity and good to excellent diastereoselectivity.[14–16] It is thought that a metal-bound nitrene species might be formed which then inserts oxidatively into saturated CÀH bonds in these reactions. Despite extensive studies of metalcatalyzed amidations of CÀH bonds, efficient and practical examples of such processes are limited. We report herein an efficient amidation reaction of saturated CÀH bonds catalyzed by silver (i).Silver complexes exhibit interesting activity, and silvercatalyzed organic transformations have attracted attention recently.[20–23] In particular, several nonradical oxidative group-transfer reactions catalyzed by silver were discovered.[24–27] We reported a disilver (i) compound (1, Scheme 1 a) that efficiently catalyzes the aziridination of olefins.[26] Surprisingly, subsequent studies showed that only this disilver