A straightforward synthesis of an aminocyclitol based on an enzymatic aldol reaction and a highly stereoselective intramolecular Henry reaction

The reactions of 4-nitroaldehydes 9 and 10 with dihydroxyacetonephosphate (DHAP) catalyzed by fructose-1,6-diphosphate aldolase from rabbit muscle were studied. Starting from 9 or 10, only one main stereomer of nitrocyclitol 8 was isolated. A highly stereoselective intramolecular cyclization (Henry reaction or nitroaldol reaction) took place under acidic conditions during the aldolase catalyzed condensation and phytase catalyzed phosphate hydrolysis coupled step. The catalytic hydrogenation of nitrocyclitol 8 yielded aminocyclitol 7, a valiolamine analogue. Its inhibition properties were evaluated towards five glycosidases. (C) 2004 Elsevier Ltd. All rights reserved.