Occurrence of the unusual 2C5(1C4) chair conformation in two carbohydrates and the reverse anomeric effect. x-ray structures of 3, 4, 5, 7-tetra-o-acetyl-2, 6-anhydro-d-glycero-d-ido-heptonamide (1) AND 3, 4, 5, 7-tetra-o-acetyl-2, 6- anhydro-d-glyceroL-gluco-heptonamide (2)

The title compounds 1 and 2 (both C15O15NH21) crystallized in the monoclinic space group P21 (Z=2)owith a=8.864(1), b=8.346(1), c=13.569(1)A, β=114.12(1), V=918.1(2)A3, D(calc)=1.358 g/cc for compound 1, and a=15.045(1), b=8.106(1), c=7.491 (1)A, β=97.23(1)o, V=906.4(3)A3 D(calc)=1.375 g/cc, for compound 2. The structures were solved by direct methods and refined by the full-matrix least squares technique to R indices of 0.040 and 0.046, respectively. Both compounds are in the α-D configuration and adopt the unusual 2C5(1C4) chair conformation with the carbamoyl groups on the anomeric carbon atoms equatorially oriented. In this conformation the orientations of the substituents are 2e, 3a, 4a, 5a and 6a in 1 and 2e, 3a, 4a, 5e and 6a in 2 which leads to unfavorable 1,3-diaxial interactions. The “reverse anomeric effect” which induces the 2C5chair conformation in these compounds, may have its origin in the unfavorable steric interactions found in the 5C2 (4C1)conformation where the carbamoyl group is axially oriented. Furthermore, the 2C5 conformation is stabilized by the N-H… intramolecular hydrogen bond between the carbamoyl nitrogen atom and the pyranosyl ring oxygen atom. Semi-empirical energy calculations reveal that the rotational freedom of the carbamoyl group is greater for the equatorial orientation (2C5) than for the axial orientation (5C2). © 1982, Taylor & Francis Group, LLC. All rights reserved.

Duke Scholars

Author Richard Gerald Brennan Biochemistry