Deoxy and deoxyfluoro analogues of acetylated methyl beta-D-xylopyranoside--substrates for acetylxylan esterases.
Four modified substrates for acetylxylan esterases, 2-deoxy, 3-deoxy, 2-deoxy-2-fluoro, and 3-deoxy-3-fluoro derivatives of di-O-acetylated methyl beta-D-xylopyranoside were synthesized via 2,3-anhydropentopyranoside precursors. Methyl 2,3-anhydro-4-O-benzyl-beta-D-ribopyranoside was transformed into methyl 2,3-anhydro-4-O-benzyl-beta-D-lyxopyranoside in three steps. The epoxide ring opening of 2,3-anhydropentopyranosides was accomplished either by hydride reduction or hydrofluorination. Methyl beta-D-xylopyranoside 2,3,4-tri-O-, 2,4-di-O-, and 3,4-di-O-acetates, and the prepared diacetate analogues were tested as substrates of acetylxylan esterases from Schizophyllum commune and Trichoderma reesei. Measurement of their rate of deacetylation pointed to unique structural requirements of the enzymes for the substrates. The enzymes differed particularly in the requirement for the trans vicinal hydroxy group in the deacetylation at C-2 and C-3 and in the tolerance to the presence of trans vicinal acetyl groups esterifying the OH group at C-2 and C-3.
Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 38 Bratislava, Slovakia. chemjama@savba.sk
Mária
M
Mastihubová
Peter
P
Biely
D000115:Acetylesterase / Q000737:chemistry*; D002236:Carbohydrate Conformation; D008759:Methylglycosides / Q000138:chemical synthesis* / Q000737:chemistry; D012567:Schizophyllum / Q000201:enzymology; D013379:Substrate Specificity; D014242:Trichoderma / Q000201:enzymology
D008759:Methylglycosides; C050519:methyl xylopyranoside; D000115:Acetylesterase; C081851:acetylxylan esterase