Asymmetric Total Synthesis of Bioactive Natural Products via Planar Chiral Enolate

详细研究了平面手性烯醇化物的不对称分子内共轭加成反应和分子内烷基化反应。通过对反应条件的考察，发现迈克尔受体部分的吸电子基团对不对称共轭加成反应的产率和产物的光学纯度有重要影响。另一方面，在不对称分子内烷基化反应中，芳环上与烯醇化物相邻的取代基和亲电残基会影响产物的产率和光学纯度。这些反应将作为生物活性天然产物全合成的关键步骤。

Asymmetric intramolecular conjugate addition reaction and intramolecular alkylation reaction via planar chiral enolates were investigated in detail. As a result of various exanimation of reaction conditions, it was found that electron-withdrawing groups in the part of Michael acceptor played an important role in yield and optical purity of products in asymmetric conjugate addition reaction. On the other hand, the substituents on aromatic ring which are adjacent to enolate and electrophilic residue were found to affect yield and optical purity of products in asymmetric intramolecular alkylation reaction. These reactions would be used in the total syntheses of bioactive natural products as a key step.