66465-22-3Relevant academic research and scientific papers
General and Stereocontrolled Approach to the Chemical Synthesis of Naturally Occurring Cyanogenic Glucosides
Moller, Birger L.,Olsen, Carl E.,Motawia, Mohammed S.
supporting information, p. 1198 - 1202 (2016/05/24)
An effective method for the chemical synthesis of cyanogenic glucosides has been developed as demonstrated by the synthesis of dhurrin, taxiphyllin, prunasin, sambunigrin, heterodendrin, and epiheterodendrin. O-Trimethylsilylated cyanohydrins were prepared and subjected directly to glucosylation using a fully acetylated glucopyranosyl fluoride donor with boron trifluoride-diethyl etherate as promoter to afford a chromatographically separable epimeric mixture of the corresponding acetylated cyanogenic glucosides. The isolated epimers were deprotected using a triflic acid/MeOH/ion-exchange resin system without any epimerization of the cyanohydrin function. The method is stereocontrolled and provides an efficient approach to chemical synthesis of other naturally occurring cyanogenic glucosides including those with a more complex aglycone structure.
Facile Synthesis of Cyanogen Glycosides (R)-Prunasin, Linamarin and (S)-Heterodendrin
Nakajima, Noriyuki,Ubukata, Makoto
, p. 453 - 458 (2007/10/03)
A facile synthetic route is described to cyanogenic glycosides (R)-prunasin, linamarin and (S)-heterodendrin from O-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)trichloroacetimidate and the corresponding α-hydroxyamides by a 3-step reaction of glycosylation, cyanohydrin formation by dehydration of carboxamides, and deprotection.
Biosynthesis of cyanohydrin glucosides from unnatural nitriles in intact tissue of Passiflora morifolia and Turnera angustifolia
Jaroszewski, Jerzy W.,Rasmussen, Anette Bolding,Rasmussen, Hanne Bregendorf,Olsen, Carl Erik,Jrgensen, Lise Bolt
, p. 649 - 654 (2007/10/03)
Passiflora morifolia, which under natural conditions contains cyanohydrin glucosides linamarin, lotaustralin and epilotaustralin, converted cyclopentanecarbonitrile, 2-cyclopentenecarbonitrile and 3- methylbutanenitrile into the corresponding cyanohydrin glucosides. Turnera angustifolia, which normally produces glucosides of cyclopentenone cyanohydrin, converted cyclopentanecarbonitrile, 2-methylpropanenitrile and 2-methylbutanenitrile, but not 3-methylbutanenitrile, into the corresponding cyanohydrin glucosides. Mixtures of epimers were produced when these glucosides contained chiral cyanohydrin carbon atoms. Feeding with cyclopentanecarbonitrile resulted in formation of 1-(β-D- glucopyranosyloxy)cyclopentanecarbonitrile, a saturated analogue of deidaclin and tetraphyllin A. Neither plant utilized cyclopropanecarbonitrile as substrate. The experiments demonstrate broad substrate specificity of nitrile hydroxylases present in these plants. A novel glycoside, 2-[6-O-(β-D- xylopyranosyl)-β-D-glucopyranosyloxy]propane (isopropyl primeveroside), was isolated from P. morifolia. The compound represents a rare example of natural isopropyl glycoside; its characterization included assignment of all 1H and (13C) NMR signals of the primeverosyl group using two-dimensional NMR methods. Biosynthesis of the isopropyl moiety of the primeveroside is unclear, but the formation of alcohols corresponding to natural cyanohydrins may be a previously unrecognized extension of the cyanohydrin biosynthesis pathway in higher plants.
Discrimination of the two diasteroisomeric glycosides heterodendrin and epi-heterodendrin by the combined use of NOE and molecular mechanics
Lankhorst, Peter P.,Smeets, Jan W.H.,Haasnoot, Cornelis A.G.
, p. 17 - 28 (2007/10/02)
The two glycosides (S)-heterodendrin and (R)-epi-heterodendrin were synthesized in a novel, one-step enzymatic synthesis, and separated by means of column chromatography.The 1H NMR spectra of the two diastereoisomers differ mainly in the chemical shift of H-2' of the side chain.At first sight the 1H NMR spectra do not allow a stereospecific assignment.It was found, however, that the NOE between the anomeric proton H-1 and H-2' of the side chain is considerably larger in epi-heterodendrin than in heterodendrin, which indicates on a time-averaged basis a smallerdistance between these two protons in epi-heterodendrin.This difference in conformational behaviour is correctly reproduced by molecular mechanics calculations, thereby offering a method for the discrimination of these two glycosides.Keywords: MM2; Cyanogenic glycoside; 3D structure; Conformational analysis; Glucosidase
