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Cyanohydrins and Aminocyanides as Key Intermediates to Various Spiroheterocyclic Sugars

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Carbohydrate-spiro-heterocycles

Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 57))

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Abstract

Derivatives with a double functionalization attract great interest in organic synthesis. The association on the same carbon atom of a nitrile group and a hydroxyl or amine function allows access to promising heterocyclic compounds of particular interest resulting from reactions taking advantage of the electrophilic character of the cyano group and the nucleophilic character of hydroxyl and amino groups. Thus, α-hydroxynitriles (cyanohydrins) or α-aminonitriles represent important classes of organic intermediates. The development of these families in glycochemistry has allowed syntheses of compounds with chain elongations (Kiliani-Fischer synthesis, Strecker synthesis) or even the preparation of chiral building blocks versatile in asymmetric syntheses of biologically active compounds or their intermediates. In this chapter, we summarize the synthesis of quaternized glycoderivatives such as cyanohydrins or glycoaminonitriles and their uses as intermediates to access spiro-heterocycles. Beyond the great structural diversity, stereochemical aspects will also be identified.

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References

  1. Bourgeois JM (1973) Synthesis of branched sugars and branched amino sugars. Helv Chim Acta 56:2879–2882

    CAS  Google Scholar 

  2. Tronchet JMJ, Bourgeois JM (1973) Isomerizations in sugar chemistry. IV. Action of nucleophilic agents on 3-C-cyanomethylene-3-deoxy-1,2:5,6-di-O-isopropylidenefuranoses. Comparison with corresponding furanos-3-uloses. Carbohydr Res 29:373–385

    CAS  Google Scholar 

  3. Bourgeois JM (1975) Synthesis of branched amino sugars. III. Synthesis and reactions of α-amino-nitrile derivatives of di-O-isopropylidene-1,2:5,6-α-D-ribo-hexofuranos-3-ulose. Helv Chim Acta 58:363–372

    CAS  Google Scholar 

  4. Rosenthal A, Cliff BL (1976) Branched-chain sugars. Reaction of 1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose with sodium cyanide and methyl nitroacetate. Can J Chem 54:543–547

    CAS  Google Scholar 

  5. Merino-Montiel P, López Ó, Fernández-Bolaños JG (2012) Unprecedented spiro-annelated sugar iso-ureas, guanidines and amidines as new families of glycosidase inhibitors. RSC Adv 2:11326–11335

    CAS  Google Scholar 

  6. Hricoviniova Z, Hricovini M (2013) A new type of rearrangement in branched-chain carbohydrates: isomerization of 3-C-branched aldoses. Carbohydr Res 370:1–8

    CAS  PubMed  Google Scholar 

  7. Calvo-Mateo A, Camarasa MJ, Diaz-Ortiz A, de las Heras FG, Alemany A (1988) Synthesis of 3′-C-cyano-3′-deoxypentofuranosylthymine nucleosides. Tetrahedron 44:4895–4903

    CAS  Google Scholar 

  8. Perez-Perez MJ, San-Felix A, Camarasa MJ, Balzarini J, de Clercq E (1992) Synthesis of {1-[2′,5′-bis-O-(tert-butyldimethylsilyl)-β-D-xylo- and β-D-ribofuranosyl]thymine}-3′-spiro-5″-{4″-amino-1″,2″-oxathiole-2″,2″-dioxyde} (TSAO). A novel type of specific anti-HIV agents. Tetrahedron Lett 33:3029–3032

    CAS  Google Scholar 

  9. Perez-Perez MJ, Camarasa MJ, Diaz-Ortiz A, San Felix A, de las Heras FG (1991) Stereospecific synthesis of branched-chain sugars by a novel aldol-type cyclocondensation. Carbohydr Res 216:399–411

    CAS  Google Scholar 

  10. Velazquez S, Chamorro C, Perez-Perez M-J, Alvarez R, Jimeno M-L, Martin-Domenech A, Perez C, Gago F, de Clercq E, Balzarini J, San-Felix A, Camarasa M-J (1998) Abasic analogs of TSAO-T as the first sugar derivatives that specifically inhibit HIV-1 reverse transcriptase. J Med Chem 41:4636–4647

    CAS  PubMed  Google Scholar 

  11. Ingate S, Perez-Perez M-J, de Clercq E, Balzarini J, Camarasa M-J (1995) Synthesis and anti-HIV-1 activity of novel TSAO-T derivatives modified at the 2′- and 5′-positions of the sugar moiety. Antivir Res 27:281–299

    CAS  PubMed  Google Scholar 

  12. Ingate S, de Clercq E, Balzarini J, Camarasa M-J (1995) Novel L-lyxo and 5′-deoxy-5′-modified TSAO-T analogs: synthesis and anti-HIV-1 activity. Antivir Res 32:149–164

    Google Scholar 

  13. Zhang HY, Yu HW, Ma LT, Min JM, Zhang LH (1998) Synthesis of 2-C-(4-aminocarbonyl-2-thiazoyl)-1,4-anhydro-L-xylitols and their fluoro derivatives. Tetrahedron Asymmetry 9:141–149

    CAS  Google Scholar 

  14. Zhang M, Zhang H, Yang Z, Ma L, Min J, Zhang L (1999) Synthesis of 3-C-(methyl β-D-xylofuranosid-3-yl)-5-phenyl-1,2,4-oxadiazole. Carbohydr Res 318:157–161

    CAS  PubMed  Google Scholar 

  15. Baer HH, Radatus B (1986) Two synthesis of 3-amino-3-deoxy-α-D-altropyranosyl 3-amino-3-deoxy-α-D-altropyranoside, a new analog of α,α-trehalose, involving reduction of a diazide and reductive amination of a diketone. Carbohydr Res 157:65–81

    CAS  PubMed  Google Scholar 

  16. Steiner B, Langer V, Bella M, Koos M (2013) Cyanohydrins from methyl 6-deoxy-2,3-O-isopropylidene-α-L-lyxo-hexofuranosid-4-ulose via Bucherer-Bergs and Strecker reactions. Carbohydr Res 369:31–37

    CAS  PubMed  Google Scholar 

  17. Koos M, Steiner B, Langer V, Gyepesova D, Durik M (2000) Preparation and structure determination of two sugar amino acids via corresponding hydantoin derivatives. Carbohydr Res 328:115–126

    CAS  PubMed  Google Scholar 

  18. Nguyen Van Nhien A, Cordonnier R, Le Bas M-D, Delacroix S, Soriano E, Marco-Contelles J, Postel D (2009) Highly functionalized, enantiomerically pure furo[x,y-c]pyrans via alkylidenecarbenes derived from sugar templates: synthesis and mechanism study via computational chemistry. Tetrahedron 65:9378–9394

    CAS  Google Scholar 

  19. Cordonnier R, Nguyen Van Nhien A, Soriano E, Marco-Contelles J, Postel D (2010) Experimental and computational investigation of the unexpected formation of β-substituted polyoxygenated furans from conveniently functionalized carbohydrates. Tetrahedron 66:736–742

    CAS  Google Scholar 

  20. Yu J, Zhang S, Li Z, Lu W, Cai M (2005) Stereoselective synthesis, structural characterization, and properties of 1,2-O-isopropylidene-3-C-(5-phenyl-1,2,4-oxadiazol-3-yl)-β-D-psicopyranose. Bioorg Med Chem 13:353–361

    CAS  PubMed  Google Scholar 

  21. Czernecki S, Dieulesaint A, Valery JM (1986) Chain extension of carbohydrates. I. Cyano-amination of 1,2:3,4-di-O-isopropylidene-α-D-galacto-hexodialdo-1,5-pyranose. J Carbohydr Chem 5:469–474

    CAS  Google Scholar 

  22. Czernecki S, Valery JM (1988) Chain-extension of carbohydrates. Part III. Stereochemical studies of the synthesis of α-amino-nitriles related to lincosamine. Carbohydr Res 184:121–130

    CAS  Google Scholar 

  23. Steiner B, Koos M, Langer V, Gyepesova D, Smrcok L (1998) 4-Amino-4-cyano-4,6-dideoxy sugar derivatives from methyl 6-deoxy-2,3-O-isopropylidene-α-L-lyxo-hexopyranosid-4-ulose via Strecker-type reaction. Carbohydr Res 311:1–9

    Google Scholar 

  24. Postel D, Nguyen Van Nhien A, Pillon M, Villa P, Ronco G (2000) Stereoselective synthesis of α-aminonitriles at non-anomeric positions of monosaccharides. Tetrahedron Lett 41:6403

    CAS  Google Scholar 

  25. Ducatel H, Nguyen Van Nhien A, Postel D (2008) Novel glycine like amino acids from glyco-α-aminonitriles as building blocks for peptide synthesis. Tetrahedron Asymmetry 19:67–81

    CAS  Google Scholar 

  26. Bera S, Chatterjee B, Mondal D (2016) Construction of quaternary stereo-centers on carbohydrate scaffolds. RSC Adv 6:77212–77242

    CAS  Google Scholar 

  27. Postel D, Nguyen Van Nhien A, Marco JL (2003) Chemistry of sulfonate- and sulfonamide-stabilized carbanions – the CSIC reactions. Eur J Org Chem 19:3713–3726

    Google Scholar 

  28. Calvo-Mateo A, Camarasa M-J, Diaz-Ortiz A, de las Heras FG (1988) Novel aldol-type cyclocondensation of O-mesyl (methylsulfonyl) cyanohydrins. Application to the stereospecific synthesis of branched-chain sugars. J Chem Soc Chem Commun 16:1114–1115

    Google Scholar 

  29. Camarasa MJ, Perez-Perez MJ, San-Felix A, Balzarini J, De Clercq E (1992) 3′-Spiro nucleosides, a new class of specific human immunodeficiency virus type 1 inhibitors: synthesis and antiviral activity of [2′,5′-bis-O-(tert-butyldimethylsilyl)-β-D-xylo- and -ribofuranose]-3′-spiro-5″-[4″-amino-1″,2″-oxathiole-2″,2″-dioxide] (TSAO) pyrimidine nucleosides. J Med Chem 35:2721–2727

    CAS  PubMed  Google Scholar 

  30. Perez-Perez MJ, San-Felix A, Balzarini J, de Clercq E, Camarasa MJ (1992) TSAO analogs. Stereospecific synthesis and anti-HIV-1 activity of 1-[2′,5′-bis-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-3′-spiro-5″-(4″-amino-1″,2″-oxathiole-2″,2″-dioxide)pyrimidine and pyrimidine-modified nucleosides. J Med Chem 35:2988–2995

    CAS  PubMed  Google Scholar 

  31. Velazquez S, Jimeno M-L, Camarasa M-J, Balzarini J (1994) Synthesis of [1-[3′,5′-bis-O-(tert-butyldimethylsilyl)-β-D-arabino- and β-D-ribofuranosyl]cytosine]-2′-spiro-5″-(4″-amino-1″,2″-oxathiole-2″,2″-dioxide). Analogs of the highly specific anti-HIV-1 agent TSAO-T. Tetrahedron 50:11013–11022

    CAS  Google Scholar 

  32. Kiritsis C, Manta S, Dimopoulou A, Parmenopoulou V, Gkizis P, Balzarini J, Komiotis D (2014) Stereoselective facile synthesis of 2′-spiro pyrimidine pyranonucleosides via their key intermediate 2′-C-cyano analogs. Evaluation of their bioactivity. Carbohydr Res 383:50–57

    CAS  PubMed  Google Scholar 

  33. Chamorro C, Luengo SM, Bonache M-C, Velazquez S, Perez-Perez M-J, Camarasa M-J, Gago F, Jimeno M-L, San-Felix A (2003) Synthesis and structural characterization of pyrimidine bi- and tricyclic nucleosides with sugar puckers conformationally locked into the eastern region of the pseudo-rotational cycle. J Org Chem 68:6695–6704

    CAS  PubMed  Google Scholar 

  34. Cordeiro A, Quesada E, Bonache M-C, Velazquez S, Camarasa M-J, San-Felix A (2006) A cyclic enamine derived from 1,2-O-isopropylidene-α-D-xylofuranose as a novel carbohydrate intermediate to achieve skeletal diversity. J Org Chem 71:7224–7235

    CAS  PubMed  Google Scholar 

  35. Alvarez R, Jimeno ML, Perez-Perez MJ, de Clercq E, Balzarini J, Camarasa MJ (1997) Synthesis and anti-human immunodeficiency virus type 1 activity of novel 3′-spiro nucleoside analogs of TSAO-T. Antivir Chem Chemother 8:507–517

    CAS  Google Scholar 

  36. Camarasa M-J, Jimeno M-L, Perez-Perez M-J, Alvarez R, Velazquez S, Lozano A (1999) Synthesis, NMR studies and theoretical calculations of novel 3-spiro-branched ribofuranoses. Tetrahedron 55:12187–12200

    CAS  Google Scholar 

  37. Moura M, Josse S, Postel D (2013) Preparation of Spiro[4.4]oxaphospholene and -azaphospholene systems from carbohydrate templates. J Org Chem 78:8994–9003

    CAS  PubMed  Google Scholar 

  38. Moura M, Josse S, Postel D (2018) Synthesis of phosphorus analogs of TSAO-T. Tetrahedron 74:4721–4727

    CAS  Google Scholar 

  39. Nguyen Van Nhien A, Tomassi C, Ducatel H, Len C, Postel D (2002) Glyco-α-aminonitriles as intermediates in organic synthesis. J Maroc Chim Heterocycl 1:1–6

    Google Scholar 

  40. Gasch C, Illangua JM, Merino-Montiel P, Fuentes J (2009) Stereocontrolled synthesis of (5+5), (5+6) and (6+6) 3-spiropseudonucleosides. Tetrahedron 65:4149–4155

    CAS  Google Scholar 

  41. Nguyen Van Nhien A, Ducatel H, Len C, Postel D (2002) Novel conformationally restricted glycoamino acids from glyco-α-aminonitriles as potent turn mimics in peptide synthesis. Tetrahedron Lett 43:3805–3808

    CAS  Google Scholar 

  42. Nguyen Van Nhien A, Villa P, Ronco G, Postel D (2001) Spiro hydantoins from D-ribose as new potent enzymatic inhibitors. J Pharm Pharmacol 53:939–943

    Google Scholar 

  43. Postel D, Nguyen Van Nhien A, Villa P, Ronco G (2001) Novel spirohydantoins of D-allose and D-ribose derived from glyco-α-aminonitriles. Tetrahedron Lett 42:1499–1502

    CAS  Google Scholar 

  44. Postel D, Nguyen Van Nhien A, Villa P, Ronco G (2001) New 4-amino-5H-2,3-dihydroisothiazole 1,1-dioxides from sugar α-amino nitriles using the CSIC reaction. Tetrahedron Lett 42:593–595

    CAS  Google Scholar 

  45. Declerck D, Josse S, Nguyen Van Nhien A, Szymoniak J, Bertus P, Postel D (2012) Reactivity of sugar α-aminonitrile derivatives under titanium-mediated cyclopropanation conditions. Tetrahedron 68:1145–1152

    CAS  Google Scholar 

  46. Bertus P, Szymoniak J (2001) New and easy route to primary cyclopropylamines from nitriles. Chem Commun 18:1792–1793

    Google Scholar 

  47. Nguyen Van Nhien A, Dominguez L, Tomassi C, Torres MR, Len C, Postel D, Marco-Contelles J (2004) Synthesis and transformations of [1,2-O-isopropylidene-α-D-erythro (and α-d-ribo)furanose]-3-spiro-3′-(4′-amino-5′H-2′,3′-dihydroisothiazole-1′,1′-dioxide) derivatives. Tetrahedron 60:4709–4727

    Google Scholar 

  48. Dominguez L, Nguyen Van Nhien A, Tomassi C, Len C, Postel D, Marco-Contelles J (2004) Synthesis of 4-amino-5-H-2,3-dihydroisothiazole-1,1-dioxide ring systems on sugar templates via carbanion-mediated sulfonamide intramolecular cyclization reactions (CSIC protocols) of glyco-α-sulfonamidonitriles. J Org Chem 69:843–856

    CAS  PubMed  Google Scholar 

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Authors and Affiliations

  1. Laboratoire de Glycochimie, des Antimicrobiens et des Agroressources (UMR7378), Amiens, France

    Solen Josse & Denis Postel

  2. Institut de Chimie de Picardie (FRE 3085), UFR des Sciences-UPJV, Amiens, France

    Solen Josse & Denis Postel

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  1. Solen Josse
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  2. Denis Postel
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Correspondence to Solen Josse .

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  1. Department of Organic Chemistry, University of Debrecen, Debrecen, Hungary

    László Somsák

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Josse, S., Postel, D. (2019). Cyanohydrins and Aminocyanides as Key Intermediates to Various Spiroheterocyclic Sugars. In: Somsák, L. (eds) Carbohydrate-spiro-heterocycles. Topics in Heterocyclic Chemistry, vol 57. Springer, Cham. https://doi.org/10.1007/7081_2019_35

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