TY - JOUR
T1 - Synthesis of (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol, a prochiral substrate for probing the catalytic functioning of glucosylases
AU - Weiser, Wolfgang
AU - Lehmann, Jochen
AU - Brewer, Curtis F.
AU - Hehre, Edward J.
N1 - Funding Information:
This study was supported by the Deutsche Forschungsgemeinschaft (to J.L.), and by Research Grant GM-25478 from the National Institute of General Medicine Sciences of the National Institute of Health (to E.J.H.).
PY - 1988/12/1
Y1 - 1988/12/1
N2 - Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.
AB - Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.
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U2 - 10.1016/0008-6215(88)84081-3
DO - 10.1016/0008-6215(88)84081-3
M3 - Article
C2 - 3214843
AN - SCOPUS:0024197159
SN - 0008-6215
VL - 183
SP - 287
EP - 299
JO - Carbohydrate Research
JF - Carbohydrate Research
IS - 2
ER -