Published as part of the Special Section on the 26^th French–Japanese Symposium on Medicinal and Fine Chemistry

Abstract

Attempts to obtain enantiomerically enriched tetrahydrofuran derivatives via an intramolecular oxy-Michael addition reaction of ε-hydroxyenone is discussed. Despite previous difficulties associated with the asymmetric induction of this reaction, which can proceed even without a catalyst, a highly efficient asymmetric induction was realized using a bifunctional organocatalyst derived from a cinchona alkaloid. The reaction could be extended to ζ-hydroxyenone to yield an optically active tetrahydropyran derivative with a high ee. In these reactions, it is important for the gentle acidic and basic sites in the bifunctional organocatalyst to be arranged properly within the molecular skeleton of the catalyst. The high performance asymmetric induction relied on the affinity of the catalyst for the substrate, which played an important role. A disubstituted tetrahydropyran synthesis could be effectively performed via kinetic resolution using ζ-hydroxyenone containing a secondary alcohol moiety using a chiral phosphoric acid catalyst.

Attempts to obtain enantiomerically enriched tetrahydrofuran derivatives via an intramolecular oxy-Michael addition reaction of ε-hydroxyenone is discussed. Despite previous difficulties associated with the asymmetric induction of this reaction, which can proceed even without a catalyst, a highly efficient asymmetric induction was realized using a bifunctional organocatalyst derived from a cinchona alkaloid. The reaction could be extended to ζ-hydroxyenone to yield an optically active tetrahydropyran derivative with a high ee. In these reactions, it is important for the gentle acidic and basic sites in the bifunctional organocatalyst to be arranged properly within the molecular skeleton of the catalyst. The high performance asymmetric induction relied on the affinity of the catalyst for the substrate, which played an important role. A disubstituted tetrahydropyran synthesis could be effectively performed via kinetic resolution using ζ-hydroxyenone containing a secondary alcohol moiety using a chiral phosphoric acid catalyst.

中文翻译：

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双功能有机催化剂的不对称环醚化

作为第26^届法日医学与精细化学研讨会特别部分的一部分出版

抽象的

尝试通过分子内氧基获得对映体富集的四氢呋喃衍生物讨论了ε-羟基烯酮的-Michael加成反应。尽管先前存在与该反应的不对称诱导相关的困难，该困难甚至可以在没有催化剂的情况下进行，但是使用衍生自金鸡纳生物碱的双官能有机催化剂实现了高效的不对称诱导。该反应可以扩展至ζ-羟基烯酮以产生具有高ee的旋光性四氢吡喃衍生物。在这些反应中，重要的是将双官能有机催化剂中的温和的酸性和碱性位点适当地布置在催化剂的分子骨架内。高性能的不对称感应依赖于催化剂对底物的亲和力，这起了重要作用。

尝试通过分子内氧基获得对映体富集的四氢呋喃衍生物讨论了ε-羟基烯酮的-Michael加成反应。尽管先前存在与该反应的不对称诱导相关的困难，该困难甚至可以在没有催化剂的情况下进行，但是使用衍生自金鸡纳生物碱的双官能有机催化剂实现了高效的不对称诱导。该反应可以扩展至ζ-羟基烯酮以产生具有高ee的旋光性四氢吡喃衍生物。在这些反应中，重要的是将双官能有机催化剂中的温和的酸性和碱性位点适当地布置在催化剂的分子骨架内。高性能的不对称感应依赖于催化剂对底物的亲和力，这起了重要作用。