lipid-a and 1-4-dideoxy-1-4-iminoarabinitol

Methyl beta-D-xylopyranoside in a mixture of N,N-dimethylformamide and 2-methoxypropene containing a little hydrogen chloride gave preponderantly the 2,3-O-isopropylidene derivative, which was readily converted into its 4-trifluoromethanesulfonate. The facile displacement of the triflate group gave a 4-azido-4-deoxy-alpha-L-arabinopyranoside derivative, and this, on mild acid treatment, was hydrolyzed to the 2,3-diol, or under more vigorous conditions to 4-azido-4-deoxy-L-arabinose. Methyl 2,3-di-O-acetyl-4-azido-4-deoxy-alpha-L-arabinopyranoside, from the diol, appears (1H-n.m.r. data) to exist as an equilibrating mixture of the 4C1 and 1C4 conformers in chloroform solution. The reduction of the azido sugar by hydrogen over Pd/C in .6M HCl yielded 4-amino-4-deoxy-L-arabinopyranose as its hydrochloride; in 0.1M HCl, further reactions occurred to give 1,4-dideoxy-1,4-imino-L-arabinitol as the final product. The aminodeoxypentose from lipid A precursor IIA, isolated from a Salmonella mutant by Raetz et al. in 1985, was shown to be identical with the synthetic aminoarabinose by t.l.c., 1H-n.m.r. spectroscopy, and g.l.c. of the acetylated reduction products.

Topics: Amino Sugars; Arabinose; Carbohydrate Conformation; Chemical Phenomena; Chemistry; Chromatography, Thin Layer; Glycolipids; Imino Furanoses; Lipid A; Magnetic Resonance Spectroscopy; Molecular Structure; Oxidation-Reduction; Salmonella typhimurium; Sugar Alcohols