Synthesis and enzyme-catalyzed hydrolysis of a radical-masked glycosylated spin-label reagent.
N1-Acetoxy-2,2,6,6-tetramethylpiperidin-4-yl 2,3,4,6-tetra-O-benzyl-alpha- and -beta-D-glucopyranosides (3-alpha, beta) and N1-acetoxy-2,2,5,5-tetramethylpyrrolin-3-oyl 2,3,4,6-tetra-O-benzyl-alpha- and -beta-D-glucopyranosylamines (9-alpha, beta) were synthesized in good yield by Schmidt's glycosylation method. Their subsequent O-debenzylation was proceeded successfully to give the desired products 1-alpha, and 1-beta in good yield, and 2-alpha in a low yield, without 2-beta by only short-timed hydrogenolysis in the presence of palladium-on-carbon (Pd-C) in a CHCl3-MeOH solvent system that included concentrated HCl. Upon enzyme-catalyzed hydrolysis, only 2-alpha was hydrolyzed by the esterase, while both of 1-alpha and 1-beta were not hydrolyzed by any other enzyme such as lipase. These 2-alpha can likely be used as a new water-soluble radical-masked glycosylated spin-label reagent.
Sato
Shingo
S
Department of Chemistry and Chemical Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yamagata, Yonezawa 992-8510, Japan. tj419@dip.yz.yamagata-u.ac.jp
Nemoto
Miho
M
Kumazawa
Toshihiro
T
Matsuba
Shigeru
S
Onodera
Jun-ichi
J
Aoyama
Masaaki
M
Obara
Heitaro
H
Kamada
Hitoshi
H
D002384:Catalysis; D004578:Electron Spin Resonance Spectroscopy; D004950:Esterases / Q000737:chemistry*; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D006031:Glycosylation; D006868:Hydrolysis; D006898:Hydroxylamines / Q000737:chemistry; D013113:Spin Labels / Q000138:chemical synthesis*
D006027:Glycosides; D006898:Hydroxylamines; D013113:Spin Labels; D004950:Esterases