Umpolung reactivity in the stereoselective synthesis of S-linked 2-deoxyglycosides.

sugars play a critical role in the biological activity of these compounds as well as their stability and solubility. [10] As a result, considerable effort has been devoted to the stereoselective synthesis of 2-deoxyglycosides and the study of their structure–activity relationships. [11] Despite the significance of 2-deoxysugar subunits, the glycosidic linkage of 2deoxyglycosides has been found to be susceptible to hydrolysis in acid media or by glycosyl hydrolases. This reactivity has made it difficult to pinpoint the biological role of these 2deoxysugars, has resulted in toxicity [12] and reduced activity [13] of the parent molecules, and has limited their use as clinical agents. Thioglycosides (S-linked glycosides), [14] in which the glycosidic oxygen atom is replaced with a sulfur atom, are resistant towards enzymatic cleavage as well as chemical degradation. Furthermore, thioglycosides maintain the biological activity of their parent O-linked glycosides and are tolerated by most biological systems. Therefore, they are an important tool for structural biology [15] and attractive therapeutic agents. Because of these characteristics, the preparation of S-linked 2-deoxysugars for comparison of their physical, chemical, and biological properties with those of their natural O-linked counterparts is beneficial. Although a number of protocols are available for the synthesis of thioglycosides, [14, 16] there is no efficient method for the

[1]  Surya B. Adhikari,et al.  Gold-Catalyzed Synthesis of 2-Deoxy Glycosides Using S-But-3-ynyl Thioglycoside Donors , 2013 .

[2]  Tsung-Che Chang,et al.  Stereoselective synthesis of S-linked α(2→8) and α(2→8)/α(2→9) hexasialic acids. , 2012, Journal of the American Chemical Society.

[3]  D. Crich,et al.  Highly stereoselective synthesis of primary, secondary, and tertiary α-S-sialosides under Lewis acidic conditions. , 2012, Organic letters.

[4]  P. Nagorny,et al.  Recent Advances in the Synthesis of Natural 2-Deoxy-β-glycosides , 2012 .

[5]  J. Rohr,et al.  Angucyclines: Biosynthesis, mode-of-action, new natural products, and synthesis. , 2012, Natural product reports.

[6]  S. Doublier,et al.  Pleiotropic effects of cardioactive glycosides. , 2011, Current medicinal chemistry.

[7]  Y. Frapart,et al.  Reductive metalation of cyclic and acyclic pseudopeptidic bis-disulfides and back conversion of the resulting diamidato/dithiolato complexes to bis-disulfides. , 2010, Inorganic chemistry.

[8]  J. F. Arens,et al.  Chemistry of acetylenic ethers. LI: Introduction of alkylthio groups into acetylenic compounds and into other compounds with reactive hydrogen atoms by means of disulphides , 2010 .

[9]  Matthew G. Beaver,et al.  Erosion of stereochemical control with increasing nucleophilicity: O-glycosylation at the diffusion limit. , 2010, The Journal of organic chemistry.

[10]  T. Lowary,et al.  Recent advances in the synthesis of 2-deoxy-glycosides. , 2009, Carbohydrate research.

[11]  Tsung-Che Chang,et al.  Synthesis of S-linked alpha(2-->9) octasialic acid via exclusive alpha S-glycosidic bond formation. , 2009, Journal of the American Chemical Society.

[12]  Xiangming Zhu,et al.  The first synthesis of a thioglycoside analogue of the immunostimulant KRN7000. , 2008, Organic letters.

[13]  V. Křen,et al.  Sweet antibiotics - the role of glycosidic residues in antibiotic and antitumor activity and their randomization. , 2008, FEMS microbiology reviews.

[14]  Li-he Zhang,et al.  Highly Direct alpha-Selective Glycosylations of 3,4-O-Carbonate-Protected 2-Deoxy- and 2,6-Dideoxythioglycosides by Preactivation Protocol. , 2008, Organic letters.

[15]  Robert A Newman,et al.  Cardiac glycosides as novel cancer therapeutic agents. , 2008, Molecular interventions.

[16]  S. Raghavendra,et al.  GaCl3-Catalyzed addition of thiols to glycals: a facile synthesis of 2-deoxy thioglycosides , 2007 .

[17]  D. Crich,et al.  On the Influence of the C2−O2 and C3−O3 Bonds in 4,6-O-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation , 2006 .

[18]  C. Méndez,et al.  The aureolic acid family of antitumor compounds: structure, mode of action, biosynthesis, and novel derivatives , 2006, Applied Microbiology and Biotechnology.

[19]  Laszlo Szilagyi and Oscar Varela,et al.  Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections , 2006 .

[20]  W. Wakarchuk,et al.  Chemical and chemoenzymatic synthesis of S-linked ganglioside analogues and their protein conjugates for use as immunogens. , 2006, Chemistry.

[21]  J. Rohr,et al.  Deoxysugar Transfer during Chromomycin A3 Biosynthesis in Streptomyces griseus subsp. griseus: New Derivatives with Antitumor Activity , 2006, Applied and Environmental Microbiology.

[22]  D. Bundle,et al.  Thiooligosaccharide conjugate vaccines evoke antibodies specific for native antigens. , 2005, Angewandte Chemie.

[23]  N. Jayaraman,et al.  Catalytic ceric ammonium nitrate mediated synthesis of 2-deoxy-1-thioglycosides. , 2004, Carbohydrate research.

[24]  F. Toste,et al.  Rhenium(V)-Catalyzed Synthesis of 2-Deoxy-α-glycosides , 2004 .

[25]  D. Bundle,et al.  S-linked ganglioside analogues for use in conjugate vaccines. , 2004, Organic letters.

[26]  B. Vauzeilles,et al.  A highly selective route to beta-C-glycosides via nonselective samarium iodide induced coupling reactions. , 2003, Organic & biomolecular chemistry.

[27]  V. Křen,et al.  Glycosides in medicine: "The role of glycosidic residue in biological activity". , 2001, Current medicinal chemistry.

[28]  A. Richardson,et al.  Lomaiviticins A and B, potent antitumor antibiotics from Micromonospora lomaivitiensis. , 2001, Journal of the American Chemical Society.

[29]  H. Driguez.  Thiooligosaccharides as Tools for Structural Biology , 2001, Chembiochem : a European journal of chemical biology.

[30]  R. Franck,et al.  The synthesis of 2-deoxyglycosides : 1988-1999 , 2000 .

[31]  R. Bernardini,et al.  Synthesis and Immunostimulating Activity of A Thioglycolipopeptide Glycomimetic As A Potential Anticancer Vaccine Derived From Tn Antigen , 2000 .

[32]  S. Rychnovsky,et al.  Synthesis, Equilibration, and Coupling of 4-Lithio-1,3-dioxanes: Synthons for syn- and anti-1,3-Diols. , 1999, The Journal of organic chemistry.

[33]  K. Ramos,et al.  Landomycin A inhibits DNA synthesis and G1/S cell cycle progression. , 1999, Bioorganic & medicinal chemistry letters.

[34]  H. Kessler,et al.  C-glycosides: A stereoselective synthesis of α- and β-C-galactosides with glycosyl dianions , 1998 .

[35]  A. Kirschning,et al.  Chemical and biochemical aspects of deoxysugars and deoxysugar oligosaccharides , 1997 .

[36]  T. Gallagher,et al.  Nucleophilic C-glycosyl donors for C-glycoside synthesis , 1997 .

[37]  H. Driguez.  Thiooligosaccharides in glycobiology , 1997 .

[38]  T. Eisele,et al.  Synthesis of the Thio‐Linked Ganglioside GM3 epitope , 1997 .

[39]  L. Hurley,et al.  Pluramycins. Old Drugs Having Modern Friends in Structural Biology , 1996 .

[40]  T. Eisele,et al.  Synthesis of a thio-linked analogue of sialyl Lewis X , 1996 .

[41]  A. Vasella,et al.  Preparation and Transmetallation of a Triphenylstannyl β-D-Glucopyranoside: A highly stereoselective route to β-D-C-glycosides via glycosyl dianions , 1994 .

[42]  J. Beau,et al.  Stereocontrolled synthesis of C-glycosides: further studies on the organolithium reagents derived from 2-deoxy-D-glucose and D-glucose. , 1994, Bioorganic & medicinal chemistry.

[43]  H. Kessler,et al.  A stereoselective synthesis of 2-acetamido-2-deoxy-C-glucosides: Glycosyl dianions as key intermediates , 1994 .

[44]  H. Kessler,et al.  Stereoselective Synthesis of C‐Glycoside with a Glycosyl Dianion , 1993 .

[45]  H. Kessler,et al.  Stereoselektive Synthese von C-Glycosiden mit einem Glycosyl-Dianion , 1993 .

[46]  M. Mihovilovic,et al.  Directed ortho lithiation of phenylcarbamic acid 1,1-dimethylethyl ester (N-BOC-aniline). Revision and improvements , 1992 .

[47]  A. Wang.  Intercalative drug binding to DNA , 1992, Current Biology.

[48]  H. Mereyala,et al.  A novel, iterative, stereoselective route to the synthesis of axially linked 2-deoxysaccharides , 1991 .

[49]  K. Nicolaou,et al.  Chemistry and Biology of the Enediyne Anticancer Antibiotics , 1991 .

[50]  K. Nicolaou,et al.  Chemie und Biologie von Endiin‐Cytostatica/Antibiotica , 1991 .

[51]  T. Ritchie,et al.  Preparation of 2-deoxy-β-d-lyxo-hexosides (2-deoxy-β-d-galactosides) , 1989 .

[52]  M. Bhupathy,et al.  Organoalkali compounds by radical anion induced reductive metalation of phenyl thioethers , 1989 .

[53]  J. Beau,et al.  Stereocontrolled preparation of C-2-deoxy-α- and -β-d-glucopyranosyl compounds from tributyl-(2-deoxy-α- and -β-d-glucopyranosyl)stannanes☆ , 1987 .

[54]  R. H. Green,et al.  Avermectins and milbemycins. , 1987, Natural product reports.

[55]  J. Lancelin,et al.  Simple generation of a reactive glycosyl-lithium derivative , 1984 .

[56]  Ming-Teh Lin,et al.  Two-flask preparation of .alpha.-lithio cyclic ethers from .gamma.- and .delta.-lactones. Reductive lithiation as a route, via radical intermediates, to axial 2-lithiotetrahydropyrans and their equilibration to the equatorial isomers , 1984 .

[57]  M. Yus,et al.  .beta.-Substituted organolithium compounds. Reaction with alkyl halides, dimethyl disulfide, and imines , 1982 .

[58]  T. Cohen,et al.  A general preparative method for .alpha.-lithioethers and its application to a concise, practical synthesis of brevicomin , 1980 .

[59]  H. Gilbert.  Effects of solvation on the nucleophilic reaction of stable carbanions with diaryl disulfides , 1980 .

[60]  L. L. Hutchinson,et al.  Alkyllithium reagents from alkyl halides and lithium radical anions , 1980 .

[61]  T. Hayasaka,et al.  Chromomycin A3 studies in aqueous solutions. Spectrophotometric evidence for aggregation and interaction with herring sperm deoxyribonucleic acid. , 1969, Biochemistry.

[62]  M. Kamiyama,et al.  Mechanism of action of chromomycin A3. II. Inhibition of RNA polymerase reaction. , 1967, Journal of biochemistry.

[63]  C. Marino,et al.  Deoxy sugars: occurrence and synthesis. , 2007, Advances in carbohydrate chemistry and biochemistry.

[64]  R. Schmidt,et al.  Synthetic routes to thiooligosaccharides and thioglycopeptides. , 2006, Chemical reviews.

[65]  A. Weymouth-Wilson.  The role of carbohydrates in biologically active natural products. , 1997, Natural product reports.

[66]  J. Rohr,et al.  ANGUCYCLINES : TOTAL SYNTHESES, NEW STRUCTURES, AND BIOSYNTHETIC STUDIES OF AN EMERGING NEW CLASS OF ANTIBIOTICS , 1997 .

[67]  D. Kahne.  Strategies for the design of minor groove binders: a re-evaluation based on the emergence of site-selective carbohydrate binders. , 1995, Chemistry & biology.

[68]  J. Lown,,et al.  Discovery and development of anthracycline antitumour antibiotics , 1993 .

[69]  J. Rohr,et al.  Angucycline group antibiotics. , 1992, Natural product reports.

[70]  S. Rychnovsky,et al.  Preparation of 2-lithiotetrahydropyrans: Kinetic and thermodynamic generation of alkyllithium reagents , 1989 .

[71]  H. H. Baer,et al.  Synthesis and biological activity of (S)-2′-fluorodaunorubicin , 1988 .

[72]  J. Beau,et al.  Stereospecific generation of α- and β-glycosyl-lithium reagents from glycosyl-stannanes: a stereocontrolled route to α- and β-C-glycosides , 1985 .

[73]  J. Beau,et al.  D-glycopyranosyl phenylsulfones: Their use in a stereocontrolledsynthesis of cis-2,6-disubstituted tetrahydropyrans (β-d-c-clycosides)☆ , 1985 .

[74]  J. Beau,et al.  Preparation and reductive lithiation of 2-deoxy-D-glucopyranosyl phenylsulfones: A highly stereoselective route to C-glycosides☆ , 1985 .