Studies on synthesis of biologically active natural indole compounds and related compounts utilized asymmetric domino reactions

我们最近开发了利用立体选择多米诺反应构建不对称季碳中心的方法，现在我们已经将我们的方法应用于不对称合成具有生物活性的吡咯[2,3-b]吲哚、假茶碱胺、氟曲明、阿莫罗明和植黑素衍生物。随着其进一步应用于叔醇的构造，我们已经接近了3-羟基吡咯[2,3-b]吲哚，氟曲明醇和碱性。由光学活性烯丙醇衍生的2-烯丙氧基吲哚-3- 1的连续烯烃、异构化和克拉森重排进行高立体选择性地得到光学活性3,3-二取代的氧吲哚，这些氧吲哚被还原为光学活性3a-烯丙基吡咯[2,3-b]吲哚。我们已经高效地完成了假茶碱胺和氟曲明A和b的不对称全合成。烯化作用与光学活性的2-allylindolin-3-ones内鎓盐,其次是异构化进行不对称克莱森重排购买高收益的旋光羟吲哚。我们成功地合成了非天然假茶碱胺。我们已经合成了3a-烯丙基phenserin作为植黑素衍生物，其大部分位于3a位置。我们建立了2-烯丙基氧吲哚-3-酮烯烯化- clisen重排法合成3-羟基氧吲哚的方法，实现了多那西啶、艾林和曲伏他啶A、B的全合成。

We recently developed the method for construction of asymmetric quarternary carbon center using stereoselective domino reactions, and now we have applied our method to asymmetric synthesis of biologically active pyrrolo[2,3-b]indoles, pseudophyrinaminol, flustramines, amauromin, and physostigumin derivatives. As its further application to construction of tertiary alcohol, we have approached to 3a-hydroxypyrrolo[2,3-b]indoles, flustraminol and alline.1.The tandem olefination, isomerization and Claisen rearrangement of 2-allyloxyindolin-3-ones, derived from optically active allyl alcohols, proceeded high-stereoselectively to give optically active 3,3-disubstituted oxindoles, which were reduced to give optically active 3a-allylpyrrolo[2,3-b]indoles. We have accomplished efficiently asymmetric total synthesis of pseudophyrinaminol and flustramines A and B.2.Olefination 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. We have succeeded in total synthesis of unnatural pseudophyrinaminol.3.We have achieved synthesis of 3a-allylphenserin as physostigumin derivative having the bulky moiety at 3a position..4.We have established the synthetic method for 3-hydroxyoxindoles utilizing enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones, and we have achieved total synthesis of donaxiridine, alline, and comvolutamydines A and B.