Mild and Efficient Hydrolysis of Thioglycosides to Glycosyl Hemiacetals Using N-Iodosaccharin [1]

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

A convenient methodology has been developed for the mild hydrolysis of thioglycosides to the corresponding hemiacetals using N-iodosaccharin without any requirement of co-activator. Most of the functional groups used for the protecting group ­manipulation of carbohydrates remain unaffected under the reaction conditions.

CDRI Communication no. 7172.

References and Notes

• 2 Schmidt RR. Kinzy W. Adv. Carbohydr. Chem. Biochem.  1994,  50:  21 ; and references therein
  PubMedGoogle Scholar
• 3 Paulsen H. Angew. Chem., Int. Ed. Engl.  1990,  29:  823 
  CrossrefGoogle Scholar
• 4 Barresi F. Hindsgaul O. J. Carbohydr. Chem.  1995,  14:  1043 
  CrossrefGoogle Scholar
• 5 Caputo R. Kunz H. Mastroianni D. Palumbo G. Pedatella S. Solla F. Eur. J. Org. Chem.  1999,  3147 
  CrossrefGoogle Scholar
• 6 Schmidt RR. Jung K.-H. In Preparative Carbohydrate Chemistry   Hanessian S. Marcel Dekker; New York: 1996.  p.283-312  
  Google Scholar
• 7a Nguyen HM. Poole JL. Gin DY. Angew. Chem. Int. Ed.  2001,  40:  414 
  CrossrefGoogle Scholar
• 7b Garcia BA. Gin DY. Org. Lett.  2000,  2:  2135 
  CrossrefGoogle Scholar
• 7c Garcia BA. Gin DY. J. Am. Chem. Soc.  2000,  122:  4269 
  CrossrefGoogle Scholar
• 8 Hanessian S. In Total Synthesis of Natural Products: The Chiron Approach   Baldwin JE. Pergamon; Oxford: 1983. 
  Google Scholar
• 9 Gothelf KV. Jørgensen KA. Chem. Rev.  1998,  98:  863 
  CrossrefPubMedGoogle Scholar
• 10 Excoffier G. Gagnaire D. Utille J.-P. Carbohydr. Res.  1975,  39:  368 
  CrossrefGoogle Scholar
• 11 Conchie J. Levvy GA. Meth. Carbohydr. Chem.  1963,  2:  345 
  Google Scholar
• 12 Tiwari P. Misra AK. Tetrahedron Lett.  2006,  47:  3573 
  CrossrefGoogle Scholar
• 13 Koto S. Morishima N. Miyata Y. Zen S. Bull. Chem. Soc. Jpn.  1976,  49:  2639 
  CrossrefGoogle Scholar
• 14 Ogawa T, Koike K, Numata M, Sugimoto M, and Nakahara M. inventors; Jpn. Patent, JP  8835591. 
• 15 Motawia MS. Marcussan J. Moeller BL. J. Carbohydr. Chem.  1995,  14:  1279 
  CrossrefGoogle Scholar
• 16 Oshitari T. Shibasaki M. Yoshizawa T. Tomita M. Takao K. Kobayashi S. Tetrahedron  1997,  53:  10993 
  CrossrefGoogle Scholar
• 17 Duynstee HI. de Koning MC. Ovaa H. van der Marel GA. van Boom JH. Eur. J. Org. Chem.  1999,  2623 
  CrossrefGoogle Scholar
• 18 Dinkelaar J. Witte MD. van den Bos LJ. Overkleeft HS. van der Marel GA. Carbohydr. Res.  2006,  341:  1723 
  CrossrefGoogle Scholar
• 19 Dasgupta S. Roy B. Mukhopadhyay B. Carbohydr. Res.  2006,  341:  2708 
  CrossrefGoogle Scholar
• 20 Uchiro H. Wakiyama Y. Mukaiyama T. Chem. Lett.  1998,  567 
  CrossrefGoogle Scholar
• 21 Bujar Barua PM. Sahu PR. Mondal E. Bose G. Khan AT. Synlett  2002,  81 
  Article in Thieme ConnectGoogle Scholar
• 22 Mondal E. Bujar Barua PM. Bose G. Khan AT. Chem. Lett.  2002,  210 
  CrossrefGoogle Scholar
• 23 Misra AK. Agnihotri G. Carbohydr. Res.  2004,  339:  885 
  CrossrefGoogle Scholar
• 24a Aloui M. Fairbanks AJ. Synlett  2001,  797 
  CrossrefGoogle Scholar
• 24b Aloui M. Fairbanks AJ. Chem. Commun.  2001,  1406 
  CrossrefGoogle Scholar
• 25 Dolenc D. Synlett  2000,  544 
  Article in Thieme ConnectGoogle Scholar
• 26 Firouzabadi H. Iranpoor N. Ebrahimzadeh F. Tetrahedron Lett.  2006,  47:  1771 
  CrossrefGoogle Scholar

CDRI Communication no. 7172.

Typical Experimental Procedure: To a solution of thioglycoside (1.0 mmol) in MeCN-H₂O (10:1; 5 mL) was added N-iodosaccharin (1.5 mmol) at r.t. and the reaction mixture was allowed to stir for the time mentioned in Table [1] . After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The crude mass was purified over SiO₂ using hexane-EtOAc as eluent to furnish the pure glycosyl hemiacetal as an anomeric mixture. Products of all known compounds gave acceptable ¹H NMR and ¹³C NMR spectra that matched the data reported in the cited references. [28]

Spectral data of selected compounds:
3- O -Acetyl-4,6- O -benzylidene-2-deoxy-2-phthalimido-d -glucopyranose (Table 1, Entry 13): ¹H NMR (300 MHz, CDCl₃): δ = 7.33-7.91 (m, 9 H, aromatic protons), 5.85 (t, J = 9.0 Hz, 1 H, H-3), 5.69 (d, J = 8.1 Hz, 1 H, H-1), 5.58 (s, 1 H, PhCH), 4.48 (dd, J = 4.5, 10.2 Hz, 1 H, H-4), 4.35-4.40 (m, 1 H, H-2), 3.70-3.83 (m, 3 H, H-5, H-6a, H-6b), 1.88 (s, 3 H, OCOMe). ESI-MS: m/z calcd for C₂₃H₂₁NO₈: 439; found: 462 [M + Na]⁺.
2,3,4,5,6-Penta- O -acetyl-d -galactose (Table 1, Entry 20): ¹H NMR (300 MHz, CDCl₃): δ = 2.04-2.12 (5 × s, 15 H), 3.91 (dd, 1 H), 4.26 (dd, 1 H), 5.26 (d, J = 2.0 Hz, 1 H), 5.36 (m, 1 H), 5.49 (d, J = 8.0 Hz, 1 H), 5.62 (d, J = 8.0 Hz, 1 H), 9.45 (br s, 1 H). ESI-MS: m/z calcd for C₁₆H₂₂O₁₁: 390; found: 413 [M + Na]⁺.