C-glycosylmethylene carbenes: synthesis of anhydro-aldose tosylhydrazones as precursors; generation and a new synthetic route to exo-glycals.

Acylated anhydro-aldononitriles (glycosyl cyanides) were transformed into anhydro-aldose tosylhydrazones by Raney-nickel reduction in the presence of tosylhydrazine in a one-pot reaction. The configuration of the C=N double bond in these hydrazones was E as proven by 15N-1H coupling constants as well as X-ray crystallography. Thermolysis in refluxing 1,4-dioxane of the sodium salts of the tosylhydrazones obtained by sodium hydride (generally 10 eq.) resulted in the formation of anhydro-1-deoxy-ald-1-enitols (exo-glycals). "Dimeric" N-glycosylmethyl anhydro-aldose tosylhydrazones could also be isolated when the use of less base caused incomplete deprotonation of the starting compounds. This two-step procedure constitutes a novel, reasonably short synthetic pathway to acylated exo-glycals from the readily available glycosyl cyanides.

[1]  L. Somsák,et al.  Preparation of 2,6-anhydro-aldose acylhydrazones, -semicarbazones and -oximes from 2,6-anhydro-aldononitriles (glycosyl cyanides). , 2003, Carbohydrate research.

[2]  Chun-Hung Lin,et al.  Stereochemistry in the synthesis and reaction of exo-glycals. , 2002, The Journal of organic chemistry.

[3]  P. Murphy,et al.  A New Route toexo-Glycals Using the Ramberg-Bcklund Rearrangement , 2002 .

[4]  Hideyo Takahashi,et al.  An efficient synthesis of new 1′-C-methyl-α-O-disaccharides using 1-methylenesugars as the glycosyl donors , 2001 .

[5]  L. Somsák,et al.  One-pot transformation of nitriles into aldehyde tosylhydrazones , 2001 .

[6]  L. Somsák,et al.  Carbanionic reactivity of the anomeric center in carbohydrates. , 2001, Chemical reviews.

[7]  K. Tatsuta,et al.  Glycoscience: Chemistry and Chemical Biology I–III , 2001 .

[8]  L. Somsák,et al.  exo-Glycals from glycosyl cyanides. First generation of C-glycosylmethylene carbenes from 2,5- and 2,6-anhydroaldose tosylhydrazones , 2001 .

[9]  Sunggak Kim,et al.  Carbene Reactions of α-Oxacyclo- and α-Azacyclo-N-aziridinylimines: Effect of Heteroatom and Ring Size in the Ring Expansion Reaction , 2000 .

[10]  Joelle M. R. Gola,et al.  Stereocontrolled Access to Higher Sugars (Non‐1‐en‐4‐ulopyranosyl Derivatives) and Glycomimetics [3‐(β‐D‐Glycopyranosyl)‐1‐propenes and(3Z)‐4,8‐Anhydro‐nona‐1,3‐dienitols] , 2000 .

[11]  W. Gerwick,et al.  One‐ and two‐dimensional gradient‐selected HSQMBC NMR experiments for the efficient analysis of long‐range heteronuclear coupling constants , 2000 .

[12]  Y. Lakhrissi,et al.  Efficient conditions for the synthesis of C-glycosylidene derivatives: a direct and stereoselective route to C-glycosyl compounds† , 2000 .

[13]  R. Franck,et al.  BENZYLIC C-GLYCOSIDES VIA THE RAMBERG-BACKLUND REACTION , 1998 .

[14]  P. Murphy,et al.  A Ramberg-Bäcklund approach to exo-glycals , 1998 .

[15]  Z. Pakulski.  Seven Membered Ring Sugars , 1996 .

[16]  Y. Chapleur,et al.  Wittig Olefination of Lactones , 1996 .

[17]  F. Xie,et al.  Synthesis and spontaneous dimerization of the tri-O-benzyl derivative of "2-keto-1-C-methylene-D-glucopyranose" (2,6-anhydro-4,5,7-tri-O-benzyl-1-deoxy-D-arabino-hept-1-en-3-ulose+ ++). , 1994, Carbohydrate research.

[18]  R. Schmidt,et al.  Glycal‐1‐ylmethylphosphonates – precursors of glycosyltransferase inhibitors , 1994 .

[19]  R. Schmidt,et al.  A new galactosyl transferase inhibitor , 1993 .

[20]  A. G. Tolstikov,et al.  Glycals in enantiospecific synthesis , 1993 .

[21]  Giovanni Luca Cascarano,et al.  Completion and refinement of crystal structures with SIR92 , 1993 .

[22]  R. Csuk,et al.  Methylenation of aldonolactones , 1991 .

[23]  T. V. RajanBabu,et al.  1-Methylene sugars as C-glycoside precursors , 1986 .

[24]  J. Lancelin,et al.  Use of selenium in carbohydrate chemistry: Preparation of C-glycoside congeners , 1985 .

[25]  C. Wilcox,et al.  A new approach to c-glycoside congeners: Metal carbene mediated methylenation of aldonolactones. , 1984 .

[26]  J. Lehmann,et al.  Diastereotopic substrates of β-d-galactosidase from Escherichia coli as probes for a catalytically active, protonating group , 1983 .

[27]  J. Watters,et al.  Synthesis of some derivatives of 2,5-Anhydro-D-mannitol , 1983 .

[28]  J. Lehmann,et al.  Attempted affinity-labelling of beta-D-galactosidase from Escherichia coli with 2,6:3,4-dianhydro-1-deoxy-D-talo-hept-1-enitol. , 1982, Carbohydrate research.

[29]  S. Hanessian,et al.  Synthesis of trans-fused perhydrofuropyrans and related α-methylene lactones: bicyclic ring-systems present in the ezomycins, the octosyl acids, and certain antitumor terpenoids☆ , 1981 .

[30]  J. Lehmann,et al.  The ineffectiveness of analogs of D-galactal as competitive inhibitors of, and substrates for, beta-D-galactosidase from Escherichia coli. , 1979, Carbohydrate research.

[31]  J. Lehmann,et al.  Spontaneous reactions of the irreversible β-D-galactosidase inhibitor 2,6-anhydro-1-deoxy-1-diazo-D-glycero-L-manno-heptitol , 1979 .

[32]  I. Farkas,et al.  Conversion of acetylated glycosyl cyanides into C-glycosyl derivatives of benzothiazole and tetrazole , 1977 .

[33]  J. Lehmann,et al.  The conversion of 2,6-anhydro-1-deoxy-d-galacto-hept-1-enitol into 1-deoxy-d-galacto-heptulose by β-d-galactosidase , 1977 .

[34]  N. Naulet,et al.  Application de l'effet α en RMN 15N et des couplages 3J 1H ≈ 15N cis trans à l'identification d'isomères géometriques Z-E autour de liaisons , 1976 .

[35]  D. Henry,et al.  Synthetic C-nucleosides: 3-(α- and β-D-arabinofuranosyl)pyrazolo[4,3-d]pyrimidine-5,7-diones , 1974 .

[36]  J. G. Moffatt,et al.  C-glycosyl nucleosides. II. A facile synthesis of derivatives of 2,5-anhydro-D-allose. , 1973, The Journal of organic chemistry.

[37]  F. Šorm,et al.  Nucleic acid components and their analogues. CLII. Synthesis of 3-(β-D-ribofuranosyl)-5,7-dihydroxy-1 H -pyrazolo[4,3- d ]pyrimidine (oxoformycin) , 1972 .

[38]  John D. Roberts,et al.  Nitrogen-15 nuclear magnetic resonance spectroscopy. XIII. Pyridine-15N , 1971 .

[39]  Z. Rappoport.  The chemistry of the cyano group , 1970 .

[40]  H. Plieninger,et al.  Weitere Beispiele der Darstellung von Aldehyden aus Nitrilen Sowie Die Synthese des 17.19‐Dihydroxy ‐ 15.16.17.18.19.20‐Hexadehydro‐Yohimbans , 1957 .

[41]  A. Dornow,et al.  Über die Alkalispaltung N‐Substituierter Benzolsulfon‐Hydrazide , 1957 .

[42]  H. Plieninger,et al.  Zur Darstellung von Aldehyd‐Derivaten aus Nitrilen , 1955 .

[43]  H. Plieninger,et al.  Einfache Methode zur Darstellung von Aldehyden , 1955 .

[44]  E. Müller.  Methoden der organischen Chemie (Houben-Weyl) , 1952 .