Solvent‐Dependent Asymmetric Synthesis of Alkynyl and Monofluoroalkenyl Isoindolinones by CpRh<sup>III</sup>‐Catalyzed C−H Activation

DOI Web Site Web Site 被引用文献4件
  • Teng Li
    School of Chemistry Sun Yat-Sen University Xingang West Road 135 Guangzhou 510275 China
  • Chao Zhou
    School of Chemistry Sun Yat-Sen University Xingang West Road 135 Guangzhou 510275 China
  • Xiaoqiang Yan
    School of Chemistry Sun Yat-Sen University Xingang West Road 135 Guangzhou 510275 China
  • Jun Wang
    School of Chemistry Sun Yat-Sen University Xingang West Road 135 Guangzhou 510275 China

書誌事項

公開日
2018-03
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/ange.201712691
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>The asymmetric synthesis of alkynyl and monofluoroalkenyl isoindolinones from N‐methoxy benzamides and α,α‐difluoromethylene alkynes is enabled by C−H activation with a chiral CpRh<jats:sup>III</jats:sup> catalyst. Remarkably, product formation is solvent‐dependent; alkynyl isoindolinones are afforded in MeOH (up to 86 % yield, 99.6 % <jats:italic>ee</jats:italic>) whereas monofluoroalkenyl isoindolinones are generated in <jats:sup>i</jats:sup>PrCN (up to 98:2 <jats:italic>Z</jats:italic>/<jats:italic>E</jats:italic>, 93 % yield, 86 % <jats:italic>ee</jats:italic>). Mechanistic studies revealed chiral allene and <jats:italic>E</jats:italic>‐configured alkenyl rhodium species as reaction intermediates. The latter is transformed into the corresponding <jats:italic>Z</jats:italic>‐configured monofluoroalkene upon protonation in the <jats:sup>i</jats:sup>PrCN system and into an alkyne by an unusual anti β‐F elimination in the MeOH system. Notably, kinetic resolution processes occur in this reaction. Despite the moderate enantiocontrol for the formation of the chiral allene, the <jats:italic>Z</jats:italic>‐monofluoroalkenyl isoindolinones and alkynyl isoindolinones were obtained in good enantiopurities by one or two sequential kinetic resolution processes.</jats:p>

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