Studies on synthesis of biologically active natural compounds, pyrrolo- and spiro-Indoles, utilized asymmetric domino reactions

在吡咯并[2，3-B]吲哚和螺吲哚类生物碱的全合成研究中，我们发展了一种立体选择性合成光学活性羟吲哚类化合物的通用有效方法，并成功地合成了所需的3 a-烯丙基吡咯并[2，3-B]吲哚和拟扑啉氨基醇的全合成.我们发展了一种合成3 a位上含有多种烯丙基结构的吡咯并[2，3-B]吲哚的通用有效方法：由几种烯丙醇衍生的2-烯丙氧基吲哚啉-3-酮经串联烯化、异构化和Claisen重排反应生成3，3-二取代羟吲哚，再经还原得到3a-烯丙基吡咯并[2，3-B]吲哚.几种2-烯丙基吲哚啉-3-酮与光学活性叶立德反应，经异构化进行不对称Claisen重排反应，高产率得到光学活性羟吲哚.阐明了在此串联反应中Claisen重排反应的立体化学.由光学活性的烯丙醇衍生的2-烯丙氧基吲哚啉-3-酮的串联反应高立体选择性地进行，得到光学活性的3，3-二取代羟吲哚。实现了由这些羟吲哚全合成光学活性假白藜芦醇。

In our studies on total synthesis of pyrrolo[2,3-b]indole and spiroindole alkaloids, we have developed the general and efficient method for stereoselective synthesis of optically active oxindoles as the synthetic key intermediates, and have succeeded in synthesis of the desired 3a-allylpyrrolo[2,3-b]indole and in total synthesis of pseudophyrinaminol.1. We have developed the general and efficient method for synthesis of pyrrolo[2,3-b]indoles having variety of allyl moiety at 3a-position ; tandem olefination, isomerization and Claisen rearrangement of 2-allyloxyindolin-3-ones, derived from several types of allyl alcohols, produced 3,3-disubstituted oxindole, which was reduced to give 3a-allylpyrrolo[2,3-b]indoles.2. The reaction of a several kind of 2-allylindolin-3-ones with optically active ylides, followed by isomerization to proceed asymmetric Claisen rearrangement to afford the optically active oxindoles in high yields.3. We make clear the stereochemisties of Claisen rearrangement in this tandem reactions.4. The tandem reactions of 2-allyloxyindolin-3-ones, derived from optically active allyl alcohols, proceeded high-stereoselectively to give optically active 3,3-disubstituted oxindoles.5. Total synthesis of optically active pseudophyrinaminol from these oxindoles was achieved.