Sulfatase-catalyzed assembly of regioselectively O-sulfonated p-nitrophenyl alpha-D-gluco- and alpha-D-mannopyranosides.
A chemoenzymic methodology is extended to the library synthesis of regioselectively O-sulfonated pNP D-gluco and D-mannopyranosides. The method involves the sequential reactions of chemical O-sulfonation and sulfatase-catalyzed O-desulfonation. pNP 2,6-di-O-sulfo-alpha-D-glucopyranoside and pNP 3,6-di-O-sulfo-alpha-D-mannopyranoside were obtained as sodium salts using chemical methods by way of dibutylstannylene acetals or tributylstannyl ethers. They were then applied to enzyme reactions using three molluscan enzymes (snail, limpet, and abalone). The sulfatase reactions cleaved a sulfate group at the secondary O-2 or O-3 position to yield the corresponding pNP 6-O-sulfo sugars. Neither pNP 6-O-sulfo-alpha-D-glucopyranoside nor 6-O-sulfo-alpha-D-mannopyranoside became the enzyme substrate. Evidently, the molluscan sulfatases have a tendency to cleave the secondary O-sulfo group with assistance from the 6-O-sulfo group.
Uzawa
Hirotaka
H
Research Center of Advanced Bionics, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi, Tsukuba 305-8565, Japan. h.uzawa@aist.go.jp
Nishida
Yoshihiro
Y
Sasaki
Kenji
K
Nagatsuka
Takehiro
T
Hiramatsu
Hideo
H
Kobayashi
Kazukiyo
K
D000818:Animals; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002384:Catalysis; D005240:Feasibility Studies; D008358:Mannose / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D008974:Mollusca / Q000201:enzymology; D013045:Species Specificity; D013379:Substrate Specificity; D013429:Sulfatases / Q000235:genetics / Q000378:metabolism*; D000520:alpha-Glucosidases / Q000138:chemical synthesis* / Q000737:chemistry
D013429:Sulfatases; D000520:alpha-Glucosidases; D008358:Mannose