Diamino-sugars

5-anhydro-3,4-diamino-pentose diethyl acetal 72 was synthesized from L-xylose by sequential reaction of epoxide and triflate intermediates with azide ion. After reduction to a 3,4-diamino-2,5-anhydroalditol, oxoruthenium(V) complexes of it and related 2,3-diamino-nucleosides (see Chapter 17) were prepared and evaluated as ribonuclease inhibitors. A number of routes were investigated for the preparation of the 2-amino-3-azido-2,3-dideoxy-D-glucoside 73, a precursor for a mimetic of the cyclopdepsipeptide didemnin B, from 2-acetamido-2-deoxy-D-glucose. Because A -deacetylation was much easier in the presence of a free 3-hydroxy-group, the best route involved preparation of a 2-deoxy-2-trifluoroacetamido-D-allopyranoside, and displacement of a mesylate group from C-3 by azide ion with inversion.  

Constantino, E. Fattonisso, A. Mangoni, M. Di Rosa, A. Inaro and P. Maffia, Tetrahedron, 1996,52,1573. 

Fukuda, T. Tanaka, M. Hirama, S. Imajo, M. Ishiguro, K. Yoshida and T. Otani, Tetrahedron Lett., 1996,37,4997. 

Braga de Oliveira and J. Dias de Soxiza Filho, Synth. Common., 1996,26,1015. 

Aligiannis, N. Pouli, P. Marakos, A.-L. Skaltsounis, S. Leonce, A. Pierre and 

1 Synthesis by Introduction of Two Amino oops. - The 2,4-diamino-2,4,6-trideoxy-L-altroside 111 was synthesized in 10 steps from L-rhamnal diacetate. 

Reagents i, MCPBA ii. TMSN3. BFyOEtz or NaNs, NH4CI 

Raic-Malic, D. Svedruzic, T. Gazivoda, A. Manmovic, A. Hergold-Brundic, A. Nagl, J. Balzarini, E. De Clercq and M. Mintas, J. Med. Chem., 2000,43,4806. 

Anilkumar, L.G. Nair, L. Olsson, J.K. Daniels and B. Fraser-Reid, Tetrahedron Lett., 2000,41,7605. 

Vieira De Almeida, E. Teixeira Cesar, A.P. Soares Fontes and E. de Castro Antunes Felicio, J. Carbohydr. Chem., 2000,19,323. 

Diaz Perez, M.I. Garcia Moreno, C. Ortiz Mellet, J. Fuentes, J.C. Diaz Arribas, F. Javier Canada and J. M. Garcia Fernandez, J. Org. Chem., 2000,65,136. 

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An attractive feature in this reaction is the possibility of direct substitution and formation of unblocked sugar derivatives containing one or more chlorodeoxy function in essentially two steps. Another facet is the formation of methyl 4,6-dichloro-4,6-dideoxy-hexosides from certain methyl glycosides in one step. Such compounds could be valuable intermediates in the synthesis of dideoxy and diamino sugars of biological importance. 

T. Komano worked with him. The work accomplished at that time included the following N-debenzyloxycarbonylation of 1,3,4,6-tetra-0-acetyl-2-(benzyloxycarbonyl)amino-2-deoxy-D-hexopyranoses in the conversion of a,/3-acetoxy to glycosyl bromide (1961) oxidative cleavages of 1,2-diamino sugars and their significance in the mechanism of the aminocarbonyl reactions (1962) and synthesis of 2-amino-2-deoxy-/3-o-glucosides via 3,4,6-tri-D-acetyl-2-benzylsulfonamido-2-deoxy-a-D-glu-copyranosyl bromide (1962). 

Rgure 10. Synthesis of trehalose-type amino and diamino sugars having the D-manno,D-manno configuration. 

A diamino sugar, 2,4-diamino-2,3,4,6-tetradeoxy-D-arafomo-hexo-pyranose (kasugamine), is a component of the antibiotic kasugamycin. Two key steps in a synthesis182 of this sugar were the preparation of a bromodeoxy sugar and a subsequent displacement reaction by azide... 

E. A. Couladouros, V. Constantinou-Kokotou, M. P. Georgiadis, and G. Kokotos, A synthesis in one reaction vessel of 2,4-diamino sugar precursors from 2,3-dideoxy-2-enopyranos-4-uloses, Carbohydr. Res., 254 (1994) 317-324. 

Secondary reactions lead to the formation of diketoseamines and diamino sugars. The formation of these compounds involves complex reactions and, in contrast to the formation of the primary products, does not occur on a mole-for-mole basis. 

From a polysaccharide of the Gram-positive organism BaciUus svbtilis, a related sugar has been isolated but not fully characterized it is a 4-acetamido-2-amino-2,4,6-trideoxyhexose. Another diamino sugar, a 2,6-diamino-2,6-dideoxyglucose, has been isolated from the antibiotic substance Neomycin. ... 

The same diamino sugar was also prepared through treatment of 5-azido-5-deoxy-2,3-0-isopropylidene-4-0-(mediylsulfonyl)-D-arabi-nose diethyl dithioacetal with sodium azide. Besides the normal reaction product of Sjv2 substitution, namely 4,5-diazido-4,5-dideoxy-2,3-0-isopropylidene-L-xylose diethyl dithioacetal, there was obtained a small proportion of 4,5-diazido-4,5-dideoxy-2,3-0-isopropyli-... 

Some glycosidic linkages have proved stable to hydrogen fluoride solvolysis. Attempts to isolate monosaccharides by solvolysis of the O-specific polysaccharide (13) of Shigella sonnet phase 1 with hydrogen fluoride and of the capsular polysaccharide (14) of Streptococcus pneumoniae type 1 failed. Prior acetylation of the free amino groups of the diamino sugar did not render the polymer susceptible to the solvolysis. 

In approaches to diamino sugars, Defoin et al. have investigated additions of various acylnitroso compounds to 1,2-dihydropyridine 15 and found some rather interesting regiochemical preferences (Scheme 3-X).39... 

Synthesis of Diamino Sugars from l,2-Diamino-l,2-dideoxyalditols. 4,5-Diace-tamido-4,5-dideoxy-L-xylose, M. L. Wolfrom, J. L. Minor, and W. A. Szarek, Carbohyd. Res., 1, 156-163 (1965). 

B. R. Baker and T. L. Hullar, Synthetic nucleosides. LXVI. Studies on the synthesis of cis-2,3-diamino sugars. VI. Neighboring group reactions with methyl 4,6-0-benzylidene-3-deoxy-2-0-methylsulfonyl-3thioureido-a-D-glucopyranoside, J. Org. Chem., 30 (1965) 4045-4048. 

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