Heptonic acids, 3-amino-3-deoxy

Heparin derivatives, 48, 200 Heptonic acid, D-glyeero-v-gulo, 21, 83 —, 2-deoxy-D-gluco-, lactone, 22 Heptonic acids, 3-amino-3-deoxy-, 66 Heptopyranosides, methyl, hydrolysis of, 29... 

Synthesis of 7-Amino-2,6-anhydro-7-deoxy-L-g/ycero-L-g /o-heptonic Acid... 

An elegant total synthesis of the semiprotected form of lincosamine was realized by Marshall and Beaudoin [116]. An aldehyde derived from destomic acid (6-amino-6-deoxy-L-g/yc ro-D-ga/acto-heptonic acid) was derived in a similar way from a L-serinal derivative via hetero Diels-Alder addition to 1-ethoxy-3-[(trimethylsilyl)oxy]-4-benzyloxy-1,3-butadiene [142]. A similar method was applied to the preparation of a semiprotected form of anhydrogalantinic acid, a component of the antibiotic galantin I [142]. 

A mimetic of a (1 2)-linked glycoside was devised by Ichikawa s group [32] using a 3-amino-2,6-anhydro-3-deoxy-heptonic acid building block to arrive at tetramer 23. A two-atom linker replacing the interglycosidic oxygen also characterizes this saccharide-peptide hybrid. A sulfated derivative of 23 blocked syncytium formation caused by HIV infection to CD4 cells at 50 pM concentration. 

Oligomerization of a 7-amino-2,6-anhydro-7-deoxy-heptonic acid results in mimetics of (1 6)-linked sugars with a three-atom instead of a two-atom linker. The sulfated tetramer 24 (O Scheme 7) turned out to exhibit /x-molar activity in the protection of MT2 cells from HIV infection [33], and was also shown to provide heparanase inhibitory activity [34]. With different location of the amide bond, a still benzyl protected /3(1 6)-linked octamer of glucosyl-uronic acid-methyl amine (Gum [35]) 25 was synthesized [36]. 

Further examples have been reported of the synthesis of aldonic acids by carbon-carbon bond-forming reactions. 2,3 4,5-Di-0-isopropylidene-D-arabinose (3) with methyl acetoacetate gave the Knoevenagel product (4), which is a branched-chain, unsaturated heptonic acid derivative. This rearranged on treatment with trifluoroacetic acid to afford the spiro-product (5) (Scheme 1). This same compound was obtainable from the 2,5-anhydroaldose derivative (6) by similar treatment. The synthesis of destomic acid, 6-amino-6-deoxy-L- /ycew-... 

Epimer Epidestomic add. 6-Amino-6-deoxy-L-g ycero-D- ico-heptonic acid C7H15NO7 225.198 Component of destomydns. 

Amino-3-deoxygnlose, A-280 2-Amino-2-deoxygnlnronic acid, A-281 2-Amino-2-deoxy-D-g/j cero-D-ga/ac/o-heptonic acid, A-282 2-Amino-2-deoxy-D-g/j cero-L-g/Mco-heptonic acid, A-283 2-Amino-2-deoxy-D-g/j c ro-D-gM/o-heptonic acid, A-284 2-Amino-2-deoxy-D-g/j c ro-D-ti/o-heptonic acid, A-285 2-Amino-2-deoxy-D-g/vc ro-L-maMMO-heptonic acid, A-286 2-Amino-2-deoxy-D-g/j c ro -D-talo -heptonic acid, A-287 6-Amino-6-deoxy-L-g/j c ro-D-gaiac/o-heptonic acid, D-389 6-Amino-6-deoxy-L-g/j c ro -D-gluco -heptonic acid, D-389... 

Amino-2-deoxy-D-g/ c ro-L-manMo-heptonic acid, A-286 Ascorbalamic acid, A-867... 

By Chain extension. — Addition of the glycine anion equivalent 3 to aldehydo-sugar derivatives such as L-arabmo-2, led to various 2-amino-2-deoxy-aldonic acids, such as 2-amino-2-deoxy-D-g/ycero-L-ga/flcto-heptonic acid 4 which was obtained in 35% overall yield (Scheme 1). ... 

Tri- and tetra-peptide analogues incorporating an a-atnino acid at the anomeric position, e.g. 33, were synthesized by way of a novel oxidative ting contraction of 2-amino-2-deoxy-heptonic acid derivative 31 to give heptulosonic acid glycosylamine 32 and its anomer (Scheme 6). The spirocyclic diketopiperazine 35 was obtained from 34 it could be 0-deprotected under acidic conditions then anomerized to the thermodynamically favoured C-2 q>imer with strong base. See also reference 3 for a general route to anomeric a-amino acids. 

Amino-2,6-anhydro-7-deoxy-L- /ycero-L- a/ac/o-heptonic acid (290) has been synthesized by way of selective ring-opening of 3,4,5-tri-0-acetyl-2,6-anhydro-D- /yceru-L-wflt no-heptaric anhydride (291) with ammonia." Daucic acid, a sugar acid present in wheat, sugar beet, and tobacco, etc.y has been identified as 2,6-anhydro-3-deoxy-D-x y/o-hept-2-enaric acid (292)." ... 

A standard displacement with azide ion, etc., has been used in the conversion of 3,4,7-tri-0-acetyl-2,6-anhydro-5-0-methanesulphonyl-D- /ycero-L-ma/jno-heptonamide (113) into 5-amino-2,6-anhydro-5-deoxy-D- /> ccro-D- w/<7-heptonic acid (114), which, after formation of the methyl ester hydrochloride, underwent polycondensation to give oligomeric or polymeric amides on treatment with methanolic sodium methoxide. Both 3-acetamido-2,3,6-trideoxy-L-hexosides (116) and (117) have been synthesized by introduction of an amino-group via azide-displacement of the allylic acetoxy-group in the glycal derivative (115) (116) and (117) are derivatives of L-acosamine and L-ristosamine, respectively. ... 

IR has been used to characterize the carbohydrate a-amino acids 2-amino-2-deoxy-D-g/ycero-D-ta/o-heptonic acid and 2-amino-2-deoxy-D-g/ycero-L-g/uco-heptonic acid. ... 

D-Glucosamine and either ammonia, 1,2-ethylenediamine, or 1,10-phenanthroline have been shown to form complexes with Co (III) ions, and the cobalt (ethylenediamine. D-glucosamine) complex is formed from the a-pyranose anonoo of the sugar. Aldose oximes on catalytic hydrogenation afford bis(polyhydroxyalkyl)amines. These compounds and their N-carboxymetbyl derivatives react with borate ions to give maciocyclic diborate esters which can sequester Ca, Cu and Cd ions. The coordination of some divalent transition metal imis to 2-amino-2-deoxy-D-g(ycero-D-gu/o-heptonic acid in aqueous solution has beat studied. ... 

Aromatic biosynthesis is regulated by feedback mechanisms. The first step in the biosynthesis of the 3 aromatic amino acids is catalysed by phospho-2-keto-3-deoxy-heptonate aldolase (EC 4.1.2.15). For each aromatic amino acid there is a separate isoenzyme which is subject both to end product inhibition and to repression of its synthesis by the correspond-... 

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