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<p>Positional alkene isomerization is a powerful reaction for moving a C=C bond from one position to another. This transformation, as a high atom-economy and easy-to-handle process, has gained increasing prominence in both organic and material chemistry. Despite these advances, the stereospecific positional alkene isomerization to achieve bidirectional chirality transfer remains challenging. We report herein a bidirectional&#xa0;stereospecific positional alkene isomerization of chiral exocyclic alkene analogues by achiral Lewis base catalysis. By using this central-to-axial chirality transfer strategy, the axially chiral <i>N</i>-indolylquinolinones can be readily obtained from one configuration to two different configurations. Mechanistic studies indicated that the competitive alkene isomerization and Michael/<i>retro</i>-Michael addition would affect the conformation of exocyclic alkenes, thus achieving the bidirectional central-to-axial chirality transfer. In addition, combining the asymmetric allylic substitution-isomerization and photocatalytic <i>Z</i>/<i>E</i> isomerization, all eight stereoisomers of diaxially chiral quinolinones could be easily obtained in high enantioselectivities and diastereselectivities.</p>

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Stereospecific positional alkene isomerization enables bidirectional central-to-axial chirality transfer

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月23日

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  • Qi Liu,
  • Jun Gu,
  • Hong-Feng Zhuang,
  • Ying He

摘要

Positional alkene isomerization is a powerful reaction for moving a C=C bond from one position to another. This transformation, as a high atom-economy and easy-to-handle process, has gained increasing prominence in both organic and material chemistry. Despite these advances, the stereospecific positional alkene isomerization to achieve bidirectional chirality transfer remains challenging. We report herein a bidirectional stereospecific positional alkene isomerization of chiral exocyclic alkene analogues by achiral Lewis base catalysis. By using this central-to-axial chirality transfer strategy, the axially chiral N-indolylquinolinones can be readily obtained from one configuration to two different configurations. Mechanistic studies indicated that the competitive alkene isomerization and Michael/retro-Michael addition would affect the conformation of exocyclic alkenes, thus achieving the bidirectional central-to-axial chirality transfer. In addition, combining the asymmetric allylic substitution-isomerization and photocatalytic Z/E isomerization, all eight stereoisomers of diaxially chiral quinolinones could be easily obtained in high enantioselectivities and diastereselectivities.