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

在吡咯[2,3-b]吲哚和螺旋吲哚生物碱的全合成研究中，我们建立了以旋光性氧吲哚为合成关键中间体的立体选择性合成的通用高效方法，并成功合成了所需的3a-烯基吡咯[2,3-b]吲哚和假碱胺的全合成。我们开发了具有不同3a位烯丙基的吡咯[2,3-b]吲哚的通用高效合成方法；从几种烯丙醇中衍生出2-烯丙基氧基吲哚-3- 1，经串联烯烃、异构化和克氏重排，得到3,3-二取代氧吲哚，并还原为3a-烯丙基吡咯[2,3-b]吲哚。的反应的几种2-allylindolin-3-ones旋光内鎓盐,其次是异构化进行不对称克莱森重排负担高yields.3光学活性羟吲哚。明确了该串联反应中clisen重排的立体化学性质。由旋光性烯丙醇衍生的2-烯丙氧基吲哚-3-酮进行了高立体选择性的串联反应，得到旋光性3,3-二取代氧吲哚。以这些氧吲哚为原料合成了具有光学活性的假茶碱胺。

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.