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

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.

carbohydrate - hydrolysis - thioglycoside - hemiacetals - N-iodosaccharin

References and Notes

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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]

<A NAME="RD25606ST-28">28</A>

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]⁺.