Development of new efficient rearrangement reactions of compounds bearing consecutive hetero atoms

我们发展了具有两个连续杂原子的化合物的新重排反应，用于高效制备高度官能化的化合物和杂环化合物。本文建立了N-三氟乙酰肼类化合物的[3，3]-σ转移重排反应合成吲哚啉和吲哚的新方法。在温和的条件下，含环戊烯环的N-三氟乙酰肼顺利地发生[3，3]-σ迁移重排，然后环合得到吲哚啉。另一方面，环己烯基N-三氟乙酰基肼和无环N-三氟乙酰基肼均以良好的产率得到吲哚。带有邻甲氧基或邻甲基的烯肼重排得到二烯亚胺。在低温下，N-三氟甲磺酰肼转化为重排产物。同样地，我们发现O-芳肟的[3，3]-σ迁移重排 关于我们 在较低温度下，在O-芳基肟醚的三氟乙酰化过程中，HRS顺利地发生，得到各种苯并呋喃。此外，在不保护羟基的情况下，以较好的总收率实现了天然苯并呋喃的短而实用的合成.邻位杂原子亚胺的重排反应我们首次报道了肟酸酯的亚氨基1，2-Wittig重排反应。这种重排的可行性取决于衬底的结构. Z-羟肟酸酯的重排反应顺利进行，以良好的产率得到2-羟基肟醚，而相应的E-异构体得到E-和Z-羟基肟醚的混合物。将该方法应用于（+）-环磷酰胺的不对称合成.胺与杂原子相邻的重排反应我们用有机锂和有机镁试剂发现了烷氧基（芳甲基）胺的消除-重排-加成反应。该方法适用于α-支链仲芳胺的制备。此外，我们还成功地合成了在生物活性化合物中广泛存在的带有氮杂环的环状化合物。少

We have developed the new rearrangement reactions of compounds with the two consecutive hetero atoms for the efficient preparations of highly functionalized compounds and heterocycles.1. The rearrangement reaction of acylenamines adjacent to a heteroatomWe have established a novel [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydrazines for synthesis of indolines and indoles. Under the mild conditions, N-trifluoroacetyl enehydrazine having a cyclopentene ring smoothly underwent [3,3]-sigmatropic rearrangement followed by cyclization to give indolines. On the other hand, both cyclohexenyl N-trifluoroacetyl enehydrazine and acyclic N-trifluoroacetyl enehydrazine gave indoles in good yield. The rearrangement of enehydrazine carrying either an o-methoxy or an o-methyl groups gave the dienylimines. The N-trifluoromethanesulfonyl enehydrazine was converted into the rearranged product at low temperature. Similarly, we have found that [3,3]-sigmatropic rearrangement of O-aryloxime et … More hers took place smoothly during the course of trifluoroacetylation of 0-aryloxime ether at lower temperature to give the various benzofurans. Furthermore, short and practical syntheses of natural benzofurans were achieved without protection of the hydroxyl group in good overall yield.2. The rearrangement reaction of imines adjacent to a heteroatomWe have developed imino 1,2-Wittig rearrangement of the hydroximates for the first time. The feasibility of this rearrangement is dependent upon the structure the substrates. The rearrangement of Z-hydroximates proceeded smoothly to give the 2-hydroxyoxime ether in good yield while the corresponding E-isomer gave a mixture of E-and Z-hydroxyoxime ethers. This method was applied to the asymmetric synthesis of (+)-cytoxazone.3. The rearrangement reaction of amines adjacent to a heteroatomWe have found domino elimination-rearrangement-addition of alkoxy(arylmethyl)amines using organolithium and organomagnesium reagent. This method is suitable for the preparation of a-branched sec-arylamines. Furthermore, we have succeeded in the synthesis of cyclic compounds carrying an azepine ring widely found in biologically active compounds. Less