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

Abstract

The tetraaldehyde 2 obtained from α,α-trehalose (1) by periodate oxidation was cyclized with nitromethane in the presence of sodium methoxide to give a mixture of 3,3′-dideoxy-3,3′-dinitro disaccharides in good yield. Acetalation of the product with benzaldehyde followed by chromatographic separation of the bisacetals afforded crystalline 4,6;4′,6′-di-O-benzylidene derivatives (3, 4, and 5) of 3-deoxy-3-nitro-α-D-glucopyranosyl 3-deoxy-3-nitro-α-D-glucopyranoside (6, 3,3′-dideoxy-3,3′-dinitro-α,α-trehalose), 3-deoxy-3-nitro-α-D-glucopyranosyl 3-deoxy-3-nitro-α-D-mannopyranoside (7), and 3-deoxy-3-nitro-α-D-mannopyranosyl 3-deoxy-3-nitro-α-D-mannopyranoside (8), respectively. Acid debenzylidenation then gave crystalline 6–8, and these were hydrogenated catalytically to produce the corresponding diamino disaccharide dihydrochlorides 9–11.