alliarinoside and trimethylsilyl-cyanide

The allelochemical alliarinoside present in garlic mustard (Alliaria petiolata), an invasive plant species in North America, was chemically synthesized using an efficient and practical synthetic strategy based on a simple reaction sequence. Commercially available 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose was converted into prop-2-enyl 2',3',4',6'-tetra-O-acetyl-β-D-glucopyranoside and subjected to epoxidation. In a one-pot reaction, ring-opening of the epoxide using TMSCN under solvent free conditions followed by treatment of the formed trimethylsilyloxy nitrile with pyridine and phosphoryl chloride, afforded the acetylated β-unsaturated nitriles (Z)-4-(2',3',4',6'-tetra-O-β-D-glucopyranosyloxy)but-2-enenitrile and its isomer (E)-4-(2',3',4',6'-tetra-O-β-D-glucopyranosyloxy)but-2-enenitrile. Deacetylation of Z- and/or E-isomers afforded the target molecules alliarinoside and its isomer.

Topics: Brassicaceae; Chemistry Techniques, Synthetic; Cyanides; Glucosides; Introduced Species; Magnetic Resonance Spectroscopy; Nitriles; North America; Stereoisomerism; Trimethylsilyl Compounds