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 of glucosylases.
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.
Weiser
W
W
Institut für Organische Chemie und Biochemie, Universität Freiburg i. Br., West Germany.
Lehmann
J
J
Brewer
C F
CF
Hehre
E J
EJ
D000107:Acetylation; D002236:Carbohydrate Conformation; D002384:Catalysis; D055598:Chemical Phenomena; D002621:Chemistry; D006026:Glycoside Hydrolases / Q000378:metabolism*; D006031:Glycosylation; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism; D013402:Sugar Alcohols / Q000138:chemical synthesis*
D013402:Sugar Alcohols; C056279:3,7-anhydro-1,2-dideoxygluco-oct-2-enitol; D006026:Glycoside Hydrolases