Conformations of 2-C:1-N-carbonyl-2-deoxy-d-glycopyranosylamines

Abstract

Geometry and molecular conformation of theN-toluenesulfonyl1 andN-acetyl-2 derivatives of peracetylated 2-C:1-N-carbonyl-2-deoxy-α-d-glucopyranosylamine were investigated with the use of X-ray diffraction methods. Compound1 (C20H23NSO10) crystallizes in the monoclinic P21 space group, withZ=2 anda=8.238(1),b=7.988(1),c=16.928(2)A, β=99.12(1)°. Compound2 (C15H19NO9) crystallizes in orthorhombic P212121 space group withZ=4 anda=8.385(1),b=8.550(1),c=24.000(2) A. Analysis of differences in bond lengths and angles between compounds1 and2 and other compounds of this class showed that the electronwithdawing effect by the residue located at the nitrogen atom can be manifested by lengthening of the β-lactam C-N bonds, with simultaneous shortening of the distance between two carbon atoms at the ring fusion. Semi-empirical calculations suggested that the title compounds displayed two positively charged centers, susceptible for attack of nucleophiles, one at the carbonyl group of β-lactam and the second at the anomeric carbon atom. Atomic charges, however, calculated for compounds1 and2 did not explain their different reaction directions during alcoholysis.