Synthesis and enzyme-catalyzed hydrolysis of a radical-masked glycosylated spin-label reagent

• Published in: Carbohydrate research Vol. 339; no. 14; pp. 2425 - 2432
• Main Authors: Sato, Shingo, Nemoto, Miho, Kumazawa, Toshihiro, Matsuba, Shigeru, Onodera, Jun-ichi, Aoyama, Masaaki, Obara, Heitaro, Kamada, Hitoshi
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier Ltd 04-10-2004
• Subjects: Catalysis; Electron Spin Resonance Spectroscopy; Enzyme-catalyzed hydrolysis; Esterase; Esterases - chemistry; Glycosides - chemical synthesis; Glycosides - chemistry; Glycosides - metabolism; Glycosylation; Hydrogenolysis; Hydrolysis; Hydroxylamine, acyl-protected; Hydroxylamines - chemistry; Imidate; Spin Labels - chemical synthesis; Spin-label reagent, acetyl-protected; Esterase; Hydrogenolysis; Enzyme-catalyzed hydrolysis; Glycosylation; Spin-label reagent, acetyl-protected; Imidate; Hydroxylamine, acyl-protected
• ISSN: 0008-6215; 1873-426X
• DOI: 10.1016/j.carres.2004.07.014

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N
1-Acetoxy-2,2,6,6-tetramethylpiperidin-4-yl 2,3,4,6-tetra-
O-benzyl-α- and -β-
d-glucopyranosides (
3-α, β) and
N
1-acetoxy-2,2,5,5-tetramethylpyrrolin-3-oyl 2,3,4,6-tetra-
O-benzyl-α- and -β-
d-glucopyranosylamines (
9-α, β) were synthesized in good yield by Schmidt’s glycosylation method. Their subsequent O-debenzylation was proceeded successfully to give the desired products
1-α, and
1-β in good yield, and
2-α in a low yield, without
2-β by only short-timed hydrogenolysis in the presence of palladium-on-carbon (Pd–C) in a CHCl
3–MeOH solvent system that included concentrated HCl. Upon enzyme-catalyzed hydrolysis, only
2-α was hydrolyzed by the esterase, while both of
1-α and
1-β were not hydrolyzed by any other enzyme such as lipase. These
2-α can likely be used as a new water-soluble radical-masked glycosylated spin-label reagent.