Catalytic Enantioselective Steglich-Type Rearrangement of Enol Lactones: Asymmetric Synthesis of Spirocyclic 1,3-Diketones

J Org Chem. 2022 Nov 18;87(22):15031-15041. doi: 10.1021/acs.joc.2c01421. Epub 2022 Nov 3.

Abstract

An example of asymmetric Steglich-type rearrangement of enol lactones is reported. This highly enantioselective acyl transfer reaction is catalyzed by chiral isothiourea at ambient temperature and provides a useful synthetic approach to access enantioenriched spirotricyclic β,β'-diketones from a broad range of indanone or tetralone-derived lactones. Preliminary mechanistic studies suggest the initial formation of an N-acylated iminium cation intermediate that induces a following facial selective condensation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Ketones*
  • Lactones*
  • Stereoisomerism

Substances

  • Lactones
  • Ketones