Subscribe to RSS
DOI: 10.1055/s-2007-977412
Mild and Efficient Hydrolysis of Thioglycosides to Glycosyl Hemiacetals Using N-Iodosaccharin [1]
Publication History
Publication Date:
03 April 2007 (online)
![](https://www.thieme-connect.de/media/synlett/200708/lookinside/thumbnails/10.1055-s-2007-977412-1.jpg)
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.
Key words
carbohydrate - hydrolysis - thioglycoside - hemiacetals - N-iodosaccharin
CDRI Communication no. 7172.
- 2
Schmidt RR.Kinzy W. Adv. Carbohydr. Chem. Biochem. 1994, 50: 21 ; and references therein - 3
Paulsen H. Angew. Chem., Int. Ed. Engl. 1990, 29: 823 - 4
Barresi F.Hindsgaul O. J. Carbohydr. Chem. 1995, 14: 1043 - 5
Caputo R.Kunz H.Mastroianni D.Palumbo G.Pedatella S.Solla F. Eur. J. Org. Chem. 1999, 3147 - 6
Schmidt RR.Jung K.-H. In Preparative Carbohydrate ChemistryHanessian S. Marcel Dekker; New York: 1996. p.283-312 -
7a
Nguyen HM.Poole JL.Gin DY. Angew. Chem. Int. Ed. 2001, 40: 414 -
7b
Garcia BA.Gin DY. Org. Lett. 2000, 2: 2135 -
7c
Garcia BA.Gin DY. J. Am. Chem. Soc. 2000, 122: 4269 - 8
Hanessian S. In Total Synthesis of Natural Products: The Chiron ApproachBaldwin JE. Pergamon; Oxford: 1983. - 9
Gothelf KV.Jørgensen KA. Chem. Rev. 1998, 98: 863 - 10
Excoffier G.Gagnaire D.Utille J.-P. Carbohydr. Res. 1975, 39: 368 - 11
Conchie J.Levvy GA. Meth. Carbohydr. Chem. 1963, 2: 345 - 12
Tiwari P.Misra AK. Tetrahedron Lett. 2006, 47: 3573 - 13
Koto S.Morishima N.Miyata Y.Zen S. Bull. Chem. Soc. Jpn. 1976, 49: 2639 - 14
Ogawa T,Koike K,Numata M,Sugimoto M, andNakahara M. inventors; Jpn. Patent, JP 8835591. - 15
Motawia MS.Marcussan J.Moeller BL. J. Carbohydr. Chem. 1995, 14: 1279 - 16
Oshitari T.Shibasaki M.Yoshizawa T.Tomita M.Takao K.Kobayashi S. Tetrahedron 1997, 53: 10993 - 17
Duynstee HI.de Koning MC.Ovaa H.van der Marel GA.van Boom JH. Eur. J. Org. Chem. 1999, 2623 - 18
Dinkelaar J.Witte MD.van den Bos LJ.Overkleeft HS.van der Marel GA. Carbohydr. Res. 2006, 341: 1723 - 19
Dasgupta S.Roy B.Mukhopadhyay B. Carbohydr. Res. 2006, 341: 2708 - 20
Uchiro H.Wakiyama Y.Mukaiyama T. Chem. Lett. 1998, 567 - 21
Bujar Barua PM.Sahu PR.Mondal E.Bose G.Khan AT. Synlett 2002, 81 - 22
Mondal E.Bujar Barua PM.Bose G.Khan AT. Chem. Lett. 2002, 210 - 23
Misra AK.Agnihotri G. Carbohydr. Res. 2004, 339: 885 -
24a
Aloui M.Fairbanks AJ. Synlett 2001, 797 -
24b
Aloui M.Fairbanks AJ. Chem. Commun. 2001, 1406 - 25
Dolenc D. Synlett 2000, 544 - 26
Firouzabadi H.Iranpoor N.Ebrahimzadeh F. Tetrahedron Lett. 2006, 47: 1771
References and Notes
CDRI Communication no. 7172.
27Typical 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]
28Spectral 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]+.