Deoxy derivatives azides

Methyl 6-amino-6-deoxy-a-D-glucopyranoside derivatives 2c were synthesized in our laboratory by a somewhat different procedure [31]. 6-0-Sulfonyl or 6-bromo-6-deoxy derivatives of methyl a-o-glucopyranoside were substituted at C-6 by sodium azide. The 6-azido-6-deoxy intermediate was then treated by acyl chlorides in the presence of triphenylphosphine (Staudinger reaction) to afford amido derivatives which were finally de-O-acetylated to give 2c. The same reaction pathway allowed the preparation of 6-alkylamido-6-deoxy-D-glucopy-ranose derivatives, starting from o-glucose [31]. 

The benzo-crown ether 22 and its ntq>htho-analogue were synthesized from the corresponding 6-bromo-6-deoxy-derivatives by azide ion displacement. They are able to sequester dopamine presumably with the assistance of hydrogen bonding between the 6-amino-group and the phenolic hydroxyl functions on dopamine. ... 

Syntheses of amino-sugar glycosides and disaccharides, including chromogenic substrates for A -acetyl-p-D-glucosaminidase, are covered in Chapter 3. Synthesis of protected 2-amino-2-deoxy-glycosyl azides is covered in Chapter 10. 2,3,6-Trideoxy-5-0-(4-nitrobenzoyl)-3-trifluoroacetamido-L-riho-hexofuranosyl bromide, a furanoid ristosamine derivative, was synthesized from L-rhamnal via intermediates reported previously (Vol.25, p.253) to effect glycosylations. ... 

Nucleophilic Displacement Reactions in Carbohydrates. Part XI. Reaction of Methyl 6-Deoxy-2,3-O-isopropylidene-4-O-methyl-sulphonyl-a-L-talopyranoside with Sodium Azide A Synthesis of L-Perosamine (4-Amino-4,6-dideoxy-L-mannose) Derivatives, J. S. Brimacombe, O. A. Ching, and M. Stacey, J. Chem. Soc. C, (1969) 1270-1274. 

In order to construct the L-asparagine derivative of per-O-acetylated 0-(2-acetamido-2-deoxy-/ -D-glucopyranosyl( 1 — 4)-2-acetamido-2-deoxy-D-glucose (7), Spinola and Jeanloz (13) used (the sensitive) silver azide for conversion of the a-chloro anomer of the chitobiose derivative 8 into the / -azido derivative 9. Kunz and associates (14,15) have accomplished the conversion of the a-chloro anomer of 8 into 9 using sodium azide in the presence of tri-n-octyl-methylammonium chloride as a phase-transfer catalyst in chloroform water. 

Warren and associates (18) have prepared a glycosyl azide derivative (15) of a heptasaccharide. This glycosyl azide was obtained from O-a-D-manno-pyranosyl-( 1 — 6)-0-[a-D-mannopyranosyl-( 1 — 3)-(9-a-D-mannopyrano syl-(l— 6)-0-a-D - mannopyranosyl - (1 — 3)] - O-fi- d - mannopyranosyl -(1 — 4) - O - (2 - acetamido - 2 - deoxy-/ -d-glucopyranosyl) - (1 — 4) - 2 -acetamido-2-deoxy-D-glucopyranose (12) by treatment of its peracetylated derivative 13 with trimethylsilyl trifuoromethanesulfonate, followed by reaction of the intermediary oxazoline 14 with trimethylsilyl azide. Reduction of the glycosyl azide 15 in the presence of Lindlar catalyst gave the glycosyla-mine derivative 16. The condensation of 16 with 1-tert-butyl N-(9-fluoren-... 

Piperidines are obtained from 5-amino-5-deoxy sugars by cycliza-tion with C-l their preparation therefore follows the general methods of preparation of such amino sugars. The 5-O-p-tolylsulfonyl- or 5-0-(methylsulfonyl)-pentoses constitute excellent starting-materials, as these sulfonyloxy groups can be replaced by azide, and the azides can be reduced to the 5-amino derivatives, which are capable of cyclization.240-251 The formation of piperidine 178 from 5-O-p-tolyI-sulfonyl-L-arabinose diethyl dithioacetal240 (176) and 177, and of 181 from benzyl 2,3-0-isopropylidene-5-0-(methylsulfonyl)-a-D-lyxofuranoside250 (179) and 180, are examples of this reaction sequence. 

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