A new and efficient entry to d-xylo-hexos-4-ulose and some derivatives thereof through epoxidation of the 3,4-hexeno derivative of diacetone-d-glucose

A new preparation of d-xylo-hexos-4-ulose (1) and of its 3-m-chlorobenzoate (2) has been devised using the epoxidation of 3-deoxy-1,2:5,6-di-O-isopropylidene-d-erythro-hex-3-enofuranose (6) as the key step. The epoxidation of 6 in CH2Cl2 furnished with high yield 1,2:5,6-di-O-isopropylidene-3-O-m-chlorobenzoyl-4-C-hydroxy-d-xylo-hexos-4-ulo-1,4-furanose as a mixture of C-4 hemiacetal anomers (7a,b), which, on acid hydrolysis, gave a tautomeric mixture of 3-O-m-chlorobenzoyl-d-xylo-hexos-4-ulose (2) with an overall 60% yield from 6. The formation of 4-C-methoxy-diacetone-d-glucose derivatives (11a,b) through epoxidation–methanolysis of 6, took place with reduced yield because of the competition between m-chlorobenzoic acid (MCBA) and methanol to the opening by attack at C-4 of the intermediate epoxide and the formation of acyclic products arising from the alternative nucleophilic attack at C-1. Acid hydrolysis of derivatives 11 gave d-xylo-hexos-4-ulose (1) with a 35% overall yield from 6. NMR analysis showed that 2 is composed, in CD3CN, mainly by a 7:3 mixture of 4-keto-α- and β-pyranose forms, while 1, in D2O, is present as a more complex mixture constituted mainly by 4-keto-α- and β-pyranoses and their respective hydrates in a 17:15:34:34 ratio.

Figure optionsDownload as PowerPoint slide