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

• Published in: International journal of molecular sciences Vol. 25; no. 15; p. 8356
• Main Authors: Galimova, Zarema, Smirnova, Irina, Lobov, Alexander, Polovyanenko, Dmitriy, Rybalova, Tatyana, Kazakova, Oxana
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 01.08.2024
• Subjects: alkyne; Alkynes - chemistry; Carboxylic Acids - chemistry; Catalysis; dammarane triterpenoids; hollongdione; hollongdionoic acid; Magnetic Resonance Spectroscopy; Mannich base; Mannich Bases - chemistry; Molecular Structure; Triterpenes - chemistry; Vinyl chloride; Vinyl Chloride - chemistry; alkyne; vinyl chloride; hollongdione; Mannich base; dammarane triterpenoids; hollongdionoic acid
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms25158356

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 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 ; 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 - were determined by X-ray analysis.