STUDIES OF BIOLOGICALLY ACTIVE NATURAL PRODUCTS CONTAINING PYRROLO [2,3-b] INDOLE UTILIZED THE ASYMMETRIC TANDEM REACTIONS

在对具有吡咯并[2，3-b]吲哚结构的生物碱、醛并[2，3-b]吲哚的全合成研究中，我们成功地合成了所需的3a-烯丙基吡咯并[2，3-b]吲哚，并首次全合成了海洋天然产物氟草胺C：1.找到了合成3a-烯丙基吡咯并[2，3-b]吲哚的新方法：2-(3，3-二甲基烯丙基)吲哚经烯化、异构化、Claisen重排等反应制得3，3-二取代吲哚，还原为3a-(1，1-甲基二烯丙基)-吡咯并[2，3-b]吲哚。2.将两种不同的取代基直接引入吲哚核3位，是合成3，3-二取代吲哚的通用方法。3.尝试了上述串联反应的不对称版本；由光学活性烯丙醇和2-溴吲哚-3-酮衍生的光学活性2-烯丙基吲哚-3-酮的烯化、异构化和Claisen重排反应，以立体选择性进行，以较好的产率得到光学活性氧吲哚。4.几种2-烯丙基吲哚-3-酮与光学活性叶立德反应，然后异构化得到非对映选择性Claisen重排得到氧吲哚，其中非对映异构体很容易被硅胶柱层析分离得到光学活性氧吲哚。

In our studies on total synthesis of alkaloids, aldeemin, amiauromine, flustramine, and peudophynrynaminol, consisting the pyrrolo[2,3-b]indole structure, we have succeeded in synthesis of the desired 3a-allylpyrrolo[2,3-b]indole and in first total synthesis of marine natural product, flustramine C ;1.We found the new methodology for synthesis of 3a-allylpyrrolo[2,3-b]indole ; the tandem reactions, olefination, isomerization, and Claisen rearrangement of 2-(3,3-dimethylallyl)indolin-3-one produced 3,3-disubstituted oxindole, which was reduced to give 3a-(1, 1-dimethylallyl)-pyrrolo[2,3-b]indole. We succeeded in the first total synthesis of marine natural product, flustramine C utilizing our methodology.2.The tandem reactions introduced directly two different substituents to 3-site of indole nucleus, and this procedure is a general method for synthesis of 3,3-disubstituted oxindoles.3.The asymmetric version of the above-mentioned tandem reactions was tried ; olefination, isomerization and Claisen rearrangement of optically active 2-allylindolin-3-one, which was derived from optical active allyl alcohol and 2-bromoindolin-3-one, proceeded stereoselectively to give optically active oxindole in good yield.4.The reaction of a several kind of 2-allylindolin-3-ones with optically active ylides, followed by isomerization to proceed diastereoselective Claisen rearrangement to afford the oxindole, of which diastereomers were easily separated by silica gel column chromatography to give optically active oxindoles.