ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A synthesis of N-acetylneuraminic acid (1) and of N-acetyl-4-epineuraminic acid (2, R = H) from 2-acetamido-4,6-O-benzylidene-1,2-dideoxy-1-nitro-D-mannopyranose (3) and 2-acetamido-1,2-dideoxy-4,6-O-isopropylidene-1-nitro-D-mannopyranose (4), respectively, is described. Michael addition of 3 and 4 to tert-butyl 2-(bromomethyl)prop-2-enoate (5) and subsequent hydrolytic removal of the NO2 group gave the 4-nonulosonate tautomers 6/7 and 8/9, respectively (Scheme). Stereoselective reduction of 6/7 and 8/9 with NaBH4/AcOH in dioxane/H2O yielded 12/13 (94:6) and 14/15 (92:8), respectively. Reduction of 6/7 and 8/9 in the absence of AcOH or in EtOH gave 12/13 (15:85) and 14/15 (15:85), respectively. Ozonolysis of 12 and 13 followed by hydrolysis gave tert-butyl neuraminate 22 and tert-butyl 4-epineuraminate 24, respectively. Ozonolysis of 14/15, separation of the products 20 and 21, and hydrolytic removal of the isopropylidene groups gave 22 and 24, respectively. The tert-butyl ester 22 was saponified to give 1, which was further characterized as the methyl ester 23. Saponification of 24 gave the crude 4-epimer of 1, which was converted into the stable Na salt 2 and also into the methyl ester 25.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19860690528
