One-Stage Pathway from Hollongdione to C17-Alkyne and Vinyl Chloride Following Mannich Bases and Carboxylic Acid

Int J Mol Sci. 2024 Jul 30;25(15):8356. doi: 10.3390/ijms25158356.

Abstract

Hollongdione is the first recorded example of the occurrence of a dammarane hexanor-triterpene in nature possessing antiviral and cytotoxic activity. Its simple one-stage transformation into compounds with terminal alkyne and vinyl chloride fragments via the interaction with phosphorus halides is reported. The copper(I)-catalyzed Mannich reaction of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20(21)-in 3 led to a series of aminomethylated products, while 17-carboxylic acid was obtained by ozone oxidation of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20-chloro-20(21)-en 4; the following direct amidation of the latter has been developed. The structures of all new molecules were established by spectroscopic studies that included 2D NMR correlation methods; the molecular structures of compounds 2-5 were determined by X-ray analysis.

Keywords: Mannich base; alkyne; dammarane triterpenoids; hollongdione; hollongdionoic acid; vinyl chloride.

MeSH terms

  • Alkynes* / chemistry
  • Carboxylic Acids* / chemistry
  • Catalysis
  • Magnetic Resonance Spectroscopy
  • Mannich Bases* / chemistry
  • Molecular Structure
  • Triterpenes / chemistry
  • Vinyl Chloride* / chemistry

Substances

  • Alkynes
  • Carboxylic Acids
  • Mannich Bases
  • Vinyl Chloride
  • Triterpenes

Grants and funding

This work was supported by the Federal Program No. 1021062311392-9-1.4.1 and No. 123011300044-5.