Divergence of carbonyl ylide reactions as a function of diazocarbonyl compound and aldehyde substituent: Dioxolanes, dioxolenes, and epoxides
Divergence of carbonyl ylide reactions as a function of diazocarbonyl compound and aldehyde substituent: Dioxolanes, dioxolenes, and epoxides
复制标题
DOI：
10.1021/jo049403y
复制
发表时间：
2004-08-06
影响因子：
3.6
通讯作者：
Doyle, MP
中科院分区：
文献类型：
--
作者：
Russell, AE;Brekan, J;Doyle, MP
重氮羰基化合物和一系列苯甲醛之间的醋酸二铑（II）催化的反应的产物表现出的羰基叶立德中间体的分子内和分子间捕获和电子效应，支配这些转换之间的竞争程度。对于重氮丙二酸二甲酯，在二氧戊环和环氧化物形成之间存在竞争，使得对于对茴香醛，仅观察到环氧化物形成，而对于对硝基苯甲醛，仅形成1，3-二氧戊环产物。与甲基重氮乙酰乙酸，分子内捕获的中间体羰基叶立德的结果在唯一的生产二氧杂环戊烯。然而，重氮乙酰乙酸甲酯的重氮乙酸乙烯酯类似物，作为其叔丁基二甲基甲硅烷氧基衍生物，在其与取代的苯甲醛的反应中仅产生环氧化物。
The products from dirhodium(II) acetate-catalyzed reactions between diazocarbonyl compounds and a series of benzaldehydes demonstrate the extent of competition between intramolecular and intermolecular trapping of carbonyl ylide intermediates and the electronic effects that govern these transformations. With dimethyl diazomalonate, competition exists between dioxolane and epoxide formation so that with p-anisaldehyde only epoxide formation is observed and with p-nitrobenzaldehyde only 1,3-dioxolane products are formed. With methyl diazoacetoacetate, intramolecular trapping of the intermediate carbonyl ylide results in the sole production of dioxolenes. However, the vinyldiazoacetate analogue of methyl diazoacetoacetate, as its tert-butyldimethlsilyloxy derivative, only produces epoxides in its reactions with substituted benzaldehydes.