AN ANOMALOUS STEREOCHEMICAL COURSE AND A COLOR PHENOMENON IN ADDITION OF ANTHRANILIC ACID TO A SUGAR NITRO OLEFIN . SYNTHESIS OF 2,3-DIAMINO-2,3-DIDEOXY-D-MANNOSE

Most additions of nucleophiles to the nitro olefin 1, methyl 4,6-0-benzylidene-2,3-dideoxy-3-nitro-β-n-erythrohex-2-enopyranoside, give products having a 2,3-diequatorial orientation of substituents (D-gluco configuration), but the 2,3-axial-equatorial orientation (D-manno configuration) may arise with anthranilic acid as addend. While this addend, when employed in a 2:1 molar ratio in the presence of a catalytic amount of potassium hydroxide, furnished methyl 4,6-0-benzylidene-2-(2-carboxyanilino)-2,3-dideoxy-3-nitro-β-D-glucopyranoside (2) in 83% yield, it gave the D-manno isomer (9) of 2 in 56% yield as the sole, isolated product when the ratio of reactants was 1:1 and the catalyst was omitted. Addition to 1 of methyl anthranilate afforded only the methyl ester (3) of 2 and not the methyl ester (10) of 9. However, either ester was obtained from its parent acid with diazomethane. The crystalline D-manno acid (9) and ester (10) are yellow, but are colorless in solution. Compound 2 was converted by several steps into methyl 2,3-diacetamido-2,3-dideoxy-β-D-glucopyranoside (8), and compound 9 was similarly converted into new, β-glycosidic derivatives of 2,3-diamino-2,3-dideoxy-D-mannose and finally into the reducing diamino sugar dihydrochloride (14). © 1969, American Chemical Society. All rights reserved.