Activated iodosylbenzene monomer as an ozone equivalent: Oxidative cleavage of carbon-carbon double bonds in the presence of water
Activated iodosylbenzene monomer as an ozone equivalent: Oxidative cleavage of carbon-carbon double bonds in the presence of water
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DOI：
10.1021/ja070179e
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发表时间：
2007-03-14
影响因子：
15
通讯作者：
Ochiai, Masahito
中科院分区：
文献类型：
--
作者：
Miyamoto, Kazunori;Tada, Norihiro;Ochiai, Masahito
本文首次报道了一种利用芳基-λ(3)-碘烷氧化裂解碳-碳双键生成羰基化合物的有效方法的进展，该方法涉及在水存在下碘代苯和HBF_4的结合。该方法是臭氧分解的一种安全替代方法。烯烃的氧化裂解可能包括迄今未知的与芳基-λ(3)-碘烷的双键直接邻位二羟基化以及随后的氧化乙二醇裂解。环状(环戊烯、环己烯等)在我们的条件下，非环烯烃可以顺利裂解。在缺电子的苯乙烯，如间硝基苯乙烯的反应中，检测到相应的环氧化物的中间产物的形成。在我们的条件下，各种芳氧杂环还经历了环氧环的氧化裂解，并以良好的产率获得了芳香醛。
Reported here for the first time are the developments of an efficient method for oxidative cleavage of carbon-carbon double bonds yielding carbonyl compounds by using aryl-lambda(3)-iodanes, which involve a combination of iodosylbenzene and HBF4 in the presence of water. The method serves as a safety alternative to ozonolysis. The oxidative cleavage of olefins probably involves the hitherto unknown direct vicinal dihydroxylations of double bonds with aryl-lambda(3)-iodanes and the subsequent oxidative glycol fissions. Cyclic (cyclopentenes, cyclohexenes, etc.) and acyclic olefins are cleaved smoothly under our conditions. In the reaction of electron-deficient styrenes such as m-nitrostyrene, intermediate formation of the corresponding epoxide was detected. A variety of aryloxiranes also undergo an oxidative cleavage of the epoxide rings under our conditions, and aromatic aldehydes were obtained in good yields