title: Synthesis of the allelochemical alliarinoside present in garlic mustard (Alliaria petiolata), an invasive plant species in North America.
abstract: 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.
authors.affiliation: Plant Biochemistry Laboratory, Department of Plant and Environmental Sciences, University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; VILLUM Research Center for 'Plant Plasticity', University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark.
authors.forename: Carl Erik
authors.initials: CE
authors.lastname: Olsen
authors.affiliation: Plant Biochemistry Laboratory, Department of Plant and Environmental Sciences, University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; VILLUM Research Center for 'Plant Plasticity', University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; Center for Synthetic Biology 'bioSYNergy', University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; Gamle Carlsberg Vej 10, DK-1799 Copenhagen V, Denmark.
authors.forename: Birger Lindberg
authors.initials: BL
authors.lastname: Møller
authors.affiliation: Plant Biochemistry Laboratory, Department of Plant and Environmental Sciences, University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; VILLUM Research Center for 'Plant Plasticity', University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark; Center for Synthetic Biology 'bioSYNergy', University of Copenhagen, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Copenhagen, Denmark. Electronic address: mosm@life.ku.dk.
authors.forename: Mohammed Saddik
authors.initials: MS
authors.lastname: Motawia
mesh_terms: D019607:Brassicaceae / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D003486:Cyanides / Q000737:chemistry; D005960:Glucosides / Q000138:chemical synthesis* / Q000737:chemistry; D058865:Introduced Species; D009682:Magnetic Resonance Spectroscopy; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D009656:North America; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry
chemical_list: D003486:Cyanides; D005960:Glucosides; D009570:Nitriles; D014297:Trimethylsilyl Compounds; C430148:alliarinoside; C058010:trimethylsilyl cyanide
keywords: Allyl β-d-glucopyranoside tetra-acetate; Deprotection; Epoxidation; Trimethylsilyl cyanide; α,β-Unsaturated nitriles