Selective amination of secoiridoid glycosides to give monomeric pyridine, dimeric pyridine, and naphthyridine alkaloids.
Treatment of the secoiridoids oleuropein (4), ligstroside (5) and methyloleoside (6) by beta-D-glucosidase in the presence of ammonium chloride led exclusively to monomeric pyridine alkaloids 7, 1, and 8. Dimeric 3,4,5-trisubstituted pyridines were obtained from methyloleoside (6) when ammonium chloride was generated in the reaction mixture by successive additions of ammonia and hydrochloric acid. The use of ammonium acetate permitted conversion of secoiridoids 4 and 5 into the naphthyridine alkaloid jasminine (3).
Ranarivelo
Y
Y
Laboratoire de Pharmacognosie de l'Université René Descartes, UMR/CNRS no. 8638, Faculté des Sciences Pharmaceutiques et Biologiques, 4 avenue de l'Observatoire, F-75006 Paris, France.
Magiatis
P
P
Skaltsounis
A L
AL
Tillequin
F
F
D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry / Q000302:isolation & purification; D000586:Amination; D000641:Ammonia / Q000737:chemistry; D002384:Catalysis; D002845:Chromatography; D005960:Glucosides / Q000737:chemistry / Q000302:isolation & purification*; D006851:Hydrochloric Acid / Q000737:chemistry; D057888:Iridoid Glucosides; D039823:Iridoids; D015394:Molecular Structure; D009287:Naphthyridines / Q000138:chemical synthesis / Q000737:chemistry / Q000302:isolation & purification; D009525:Niacin / Q000031:analogs & derivatives / Q000737:chemistry / Q000302:isolation & purification; D019906:Nuclear Magnetic Resonance, Biomolecular; D029592:Oleaceae / Q000737:chemistry*; D011714:Pyrans / Q000737:chemistry / Q000302:isolation & purification*; D011725:Pyridines / Q000737:chemistry / Q000302:isolation & purification*; D001617:beta-Glucosidase / Q000378:metabolism
C445383:4,4'-bis-methyl-5,5'-((1-methyltrimethylene)di)methylnicotinate; C445382:4-hydroxyphenylethyl-5-ethyl-3-methoxycarbonyl-4-pyridineacetate; D000470:Alkaloids; D005960:Glucosides; D057888:Iridoid Glucosides; D039823:Iridoids; D009287:Naphthyridines; D011714:Pyrans; D011725:Pyridines; C445384:jasminine; C445381:methyloleoside; D009525:Niacin; C002769:oleuropein; D000641:Ammonia; C445380:ligstroside; D001617:beta-Glucosidase; D006851:Hydrochloric Acid