2.3- Diamino-2,3-dideoxy derivatives

R. D. Guthrie and D. Murphy, Nitrogen-containing carbohydrate derivatives. Part IX. Synthesis of 2,3-diamino-2,3-dideoxy derivatives, J. Chem. Soc. p. 6956 (1965). 

The 2,5-diamino-2,5-dideoxy derivatives of l,4 3,6-dianhydro-D-mannitol and -D-glucitol gave, on deamination, the same product, namely, l,4 3,6-dianhydro-L-iditol, in unspecified yield.176 The product presumably arose from carbonium-ion intermediates, which reacted predominantly with solvent on the less hindered, exo sides of the V-shaped molecule. 

Sulfonic esters of sugar alcohols often react similarly with ammonia thus, l,4 3,6-dianhydro-2,5-di-0-tosyl-D-mannitol and -sorbitol give326 the corresponding 2,5-diamino-2,5-dideoxy derivatives. However, 1,4 3,6-dianhydro-L-iditol affords326 a compound thought to be 1,4 3,6-dianhydro-2,5-dideoxy-2,5-imino-D-mannitol. 

It appears probable that the aldimine II, initially formed by hydrogenation of the nitrile group, is itself in the stabilized, cyclic-hemiacetal form as a 1,2-diamino-l, 2-dideoxy derivative (III), the 1-amino group of which is subsequently hydrolyzed to yield the cyclic 2-amino-2-deoxy sugar (IV) directly.10 10a... 

The deamination of the 2,5-diamino-l, 4 3,6-dianhydro-2,5-dideoxy derivatives of L-iditol and of D-glucitol has been observed to yield some 1,4 3,6- dianhydro-L-iditol in each case. The reactions evidently follow the SnI mechanism often observed in deaminations of simple aliphatic amines, and afford the product of the most stable type, with two exo hydroxyl groups. 

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. 

Compound 278 was convertible into 2-amino-2-deoxy- (280) and 2,7-diamino-2,7-dideoxy-a-DL-carba-glucopyranose (281) derivatives in satisfactory yields. 

J. Hill, L. Hough, and A. C. Richardson, Nucleophilic replacement reactions of sulphonates. I. The preparation of derivatives of 4,6-diamino-4,6-dideoxy-D-glucose and -D-galactose, Carbohydr. Res., 8 (1968) 7-18. 

The question then arises if a regioselective opening of a 2,3-rraMS-epoxy carboxamide derived from aldonic acids would occur. The 2,5-di-O-tosyl-D-ribono-1,4-lactone (62) (Scheme 13) was used to find an answer to this question. If treated with ammonia, the 2,5-diamino-2,5-dideoxy-D-ribono-1,5-lactam (63) was obtained as the only product [79]. The NMR spectra of the reaction mixture showed the formation of the diepoxy amide A which was opened at C-5 by ammonia. In this case no internal lactamization could occur, due to the trans 2,3-epoxy group in B (Scheme 13). Thus, a regioselective opening of an acyclic 2,3-epoxy carboxamide took place at C-2. The reaction was complete within 6 days. 

The deamination of derivatives of paromobiosamine [3-0-(2,6-diamino-2,6-dideoxy-/3-L-idopyranosyl)-D-ribose (16)] was used in the elucidation of the structure of the disaccharide, although the interpretation of the results was not straightforward.105 The deamination of the methyl glycoside (17) of this disaccharide106 was first... 

Wolfrom, M L, Chakravarty, P, Horton, D, Amino derivatives of starches. 2,6-Diamino-2,6-dideoxy-D-mannose dihydrochloride, J. Org. Chem., 30, 2728-2731, 1965. 

The course of ammonolysis of 111 is rather complicated, and the reaction results in a mixture containing 2,4-diamino-l,6-anhydro-2,4-dideoxy-j8-D-glucopyranose756 (154) (compare Ref. 513) and 1,6-an-hydro-3,4-dideoxy-3,4-epimino-/3-D-altropyranose756 (153) as the major products. This reaction course may be most satisfactorily explained by the sequence 111—>151 152, where 4-amino-1,6 2,3-dianhydro-4-deoxy-/3-D-mannopyranose (152) partly isomerizes (see Sect. VI,2) to the epimine 153, and partly reacts with ammonia to give740 the diamino derivative 154. 

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