Cyclizations of Dialdehydes With Nitromethane: Xiii. Synthesis of Trehalose-Type Disaccharides Containing Nitrogenous Heptuloses

Abstract

The dialdehyde I1 that arises from a partial lead tetraacetate cleavage of sucrose has been cyclized with nitromethane to give a stereoisomeric mixture of nitro disaccharides IV via their sodium nitronates 111. Upon catalytic hydrogenation a single amino disaccharide, a-D-glucopyranosyl 4-amino-4-deoxy-P-~-gluco-heptulopyra1loside hydrochloride (V), was isolated. Various derivatives of the nitrogenous heptulose components of IV and V were prepared by methanolysis and hydrolysis. The configuration of V was established by a degradation of its N-acetyIated hydrolysis product, 4-acetarnido-4-deoxy-a-D-gluco-heptulose (VII), which gave 2-arnino-2-deoxy-D-arabinose hydrochloride, and by reduction of VII, which gave the two epimeric acetanlido heptitols XI I1 and XIV.

Synthesis of the 3,3′-dinitro and 3,3′-diamino derivatives of α,α-trehalose and its D-gluco, D-manno and D-manno, D-manno isomers

“…and D-n~mrrro configurations n ould be favored under the collditiorls of kinetic co~itrol that were eniployed (16,18,19). This proved in fact to be the case.…”