Aminodeoxy sugars 3- amino-3-deoxy

The bromodeoxyaldonolactones have been used for the preparation of aminodeoxy aldonic acids and aminodeoxy sugars via azido derivatives (45,46). Likewise, a- and /J-aminopolyhydroxy acids have been prepared by treatment of the bromodeoxyaldonolactones with liquid ammonia (47). Thus, 3-amino-3-deoxy-D-threonic acid and 3-amino-3-deoxy-D-arabin-onic acid (40b) were obtained from 2-bromo-2-deoxy-L-threono- or D-xy-lono-1,4-lactone (38). It was shown that 2,3-epoxy carboxamides (namely, 39) are intermediates of the reaction. Heating at 90° for long periods led to the 3-amino-3-deoxyaldonamides, which upon acid hydrolysis yielded the corresponding aldonic acids. 

Scheme 6 Putative early common steps in the formation of deoxysugar and aminodeoxy-sugars in anthracydine biosynthesis. Glucose-3-phosphate is converted to dTDP-4-keto-2,6-deoxy-D-glucose and dTDP-3-amino-2,3,6-deoxy-4-keto-D-glucose via an instable 3,4-diketointermediate...

The action of ammonia or amines on the epoxy sugars results in ring opening with the formation of aminodeoxy sugars or their derivatives. An interesting example is found in the conversion of D-xylose to 3-amino-3-deoxy-D-ribose, a structural component of the antibiotic puromycin (80). The transformation (see formulas on p. 392) is remarkable in that derivatives of all four D-aldopentoses are involved. 

The methyl 4,6-0-benzylidene-2, S-dideoxy-S-C-nitro-iS-D-er /i/iro- and -threo-hex-2-enosides can be prepared by a facile elimination of acetic acid from the appropriate 2-0-acetyl-3-deoxy-3-C-nitro compounds they add hydrogen, ammonia, acids, and alcohols to give pyranoside products having deoxy, aminodeoxy, acyloxy, and alkoxy groupings at C-2 A wide variety of 3-amino-3-deoxy sugar derivatives may therefore be synthesized from these unsaturated compounds. 

Vogel and co-workers have synthesised a variety of aminodeoxy- and deoxy-sugars from the chiral Diels-Alder adducts of furan with cyanovinyl (IR)- or (IS)-camphanate. The adduct (56) has been converted to the lactones (57)-(59) by electrophilic functionalisation of the alkene and the masked o-keto-position, and Baeyer-Villiger oxidation, and thence into the hydrochlorides (60)-(62) of D-lividosamine, allonojirimycin, and the methyl a-glycoside of 3-amino-3-deoxy-D-... 

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