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

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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.