Organic Reactions Catalyzed by Methylrhenium Trioxide: Reactions of Ethyl Diazoacetate and Organic Azides
Organic Reactions Catalyzed by Methylrhenium Trioxide: Reactions of Ethyl Diazoacetate and Organic Azides
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DOI：
10.1021/ja954039t
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发表时间：
1996-10
影响因子：
15
通讯作者：
Zuolin Zhu;J. Espenson
中科院分区：
文献类型：
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作者：
Zuolin Zhu;J. Espenson
三氧化二甲基铼（CH3ReO3或MTO）催化重氮乙酸乙酯、EDA的几种反应。它是第一个用于碳转移的高价氧配合物。在温和的条件下，在没有其他底物的情况下，EDA转化为马来酸二乙酯和富马酸二乙酯的9:1混合物。在醇的存在下，得到了收率较高的α-烷氧基乙酸乙酯。当原料为马来酸二乙酯和富马酸酯时，较大且支链较多的醇的产率下降。苯酚对位上的给电子基团有利于α-苯氧基乙酸乙酯的形成。另一方面，利用EDA生成α-硫代乙酯和n -取代甘氨酸乙酯几乎不受母体硫醇或胺的大小或结构的影响，所有这些反应都以高收率进行。mto催化的环加成反应发生在EDA和芳香亚胺、烯烃和羰基化合物之间。形成三元环产物：叠氮嘧啶、环…
Methylrhenium trioxide (CH3ReO3 or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, α-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of α-phenoxy ethyl acetates. The use of EDA to form α-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cycl...