Total Synthesis of the 2,5-Disubstituted γ-Pyrone E1 UAE Inhibitor Himeic Acid A

Org Lett. 2023 Oct 20;25(41):7502-7506. doi: 10.1021/acs.orglett.3c02761. Epub 2023 Oct 6.

Abstract

The first total synthesis of the E1 ubiquitin-activating enzyme inhibitor, himeic acid A, is reported. A McCombie reaction was used to form the core γ-pyrone via a 6π-electrocyclization. A dioxenone ring-opening/acyl ketene trapping reaction with a primary amide provided the unusual unsymmetrical imide functionality. Other key steps include the use of an Evans auxiliary alkylation (d.r. ≥ 95:5) to install the (S)-2-methyl succinic acid fragment and a cross-metathesis to install the unsaturated side-chain.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkylation
  • Fatty Acids, Unsaturated*
  • Pyrones* / pharmacology
  • Ubiquitin-Activating Enzymes / metabolism

Substances

  • himeic acid A
  • Pyrones
  • Fatty Acids, Unsaturated
  • Ubiquitin-Activating Enzymes