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

我们开发了新的化合物与两个连续杂原子的重排反应，用于高效制备高官能化化合物和杂环。我们建立了一种新的[3,3]- n -三氟乙酰基肼的异位重排反应，用于合成吲哚和吲哚。在温和条件下，具有环戊烯环的n -三氟乙酰乙肼顺利地进行了[3,3]-异位重排，然后环合得到吲哚。另一方面，环己烯基n -三氟乙酰肼和无环n -三氟乙酰肼均能产生吲哚。携带邻甲氧基或邻甲基的炔联胺重排得到二烯基。n -三氟甲磺酰乙肼在低温下转化为重排产物。同样，我们发现0-芳酰肟醚在较低温度下三氟乙酰化得到各种苯并呋喃的过程中，o -芳酰肟等的[3,3]-异位重排更加顺利。此外，在不保护羟基的情况下，实现了短时间和实用的天然苯并呋喃的合成，总产率较高。邻杂原子亚胺的重排反应。我们首次开发了邻杂原子亚胺的1,2- wittig重排反应。这种重排的可行性取决于底物的结构。z -羟基肟酸酯的重排顺利进行，得到2-羟基肟醚，收率高，而相应的e -异构体得到e -和z -羟基肟醚的混合物。该方法应用于(+)-环恶唑酮的不对称合成。邻杂原子胺的重排反应我们用有机锂和有机镁试剂发现了烷氧基（芳基甲基）胺的多米诺骨牌消除-重排-加成反应。该方法适用于甲支二芳胺的制备。此外，我们还成功合成了在生物活性化合物中广泛存在的带有氮平环的环状化合物。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