Synthesis of D-erythro-2-pentulose and D-threo-2-pentulose and analysis of the 13C- and 1H-n.m.r. spectra of the 1-13C- and 2-13C-substituted sugars.

ABSTRACT

The pentuloses D-erythro-2-pentulose (1) and D-threo-2-pentulose (2) and their 1-13C- and 2-13C-substituted derivatives were prepared by hydrogenating the corresponding isotopically normal and 13C-substituted D-pentos-2-uloses with a Pd-carbon catalyst. The threo isomer and its labeled derivatives were alternatively prepared from isotopically normal and 13C-substituted D-xyloses with immobilized D-xylose (D-glucose) isomerase (E.C.5.3.1.5). The equilibrium compositions of 1 and 2 (furanose anomers and acyclic keto forms) in 2H2O were determined from 13C-n.m.r. spectra (75 MHz) of the 2-13C-labeled derivatives. The conformational properties of the cyclic and acyclic forms in 2H2O were assessed with the use of 1H-1H, 13C-1H, and 13C-13C spin-coupling constants obtained from 1H-n.m.r. (620 MHz) and 13C-n.m.r. (75 MHz) spectra. Compared with the structurally related aldotetrofuranoses the 2-pentulofuranoses more strongly prefer conformations in which the anomeric hydroxyl group is oriented quasi-axially. The strongly dipolarized carbonyl group in the acyclic keto forms of 1 and 2 appears to stabilize chain conformations having O-1 and O-3 eclipsed with the carbonyl oxygen.