2.3.6- Trideoxy-3-

Trideoxy-3-C-methyl-4-Omethyl-3-nitro-L-arab/no-hexopyranose... 

Trideoxy-3-C-methyl-4-0-methyl-3-nitro-D-/yxo-hexopyranose (nitrogen has priority over carbon for determining configuration)... 

C51H83IN2016-2 H20 2,3,6-Trideoxy-3-(dimethylamino)-4-0-(4-iodobenzoyl)-L-rtho-hexose, dihydrate [4-0-(4-iodobenzoyl)megalomicin A, dihydrate] IBMEGC10 43 273... 

CuH2iN04 Methyl 3-acetamido-2,3,6-trideoxy-3-C-methyl-4-0-methyl-/3-L-xy/o-hexopyranoside (MADXHP)63 Depiction at bottom of p. 444... 

Attempted direct extension of the two foregoing methodologies to synthesis of the 3-C-methyl analogs of 17, 18, 23 and 24 starting from the diastereoisomeric methyl ketones 10 and 12 was ineffective, as ammonia does not add across the triply substituted double bond of the 3-C-methyl analogs of the esters 19 and 20. However, the phenyl-sulfenimines 25 and 26 add allylmagnesium bromide and diallylzinc with different stereochemistry (8), so that it is possible to have eventual access to the four configurational isomers of 3-amino-2,3,6-trideoxy--3-C-methyl-3-L-hexose. 

Auf ahnliche Weise konnen aus Amino-zuckern Nitro-zucker hergestellt werden. So erhalt man Methyl-3-nitro-2,3,6-trideoxy-3-c-methyl-a-D-ribo-hexopyranosid aus der ent-sprechenden Amino-Verbindung mit 3-Chlor-perbenzoesaure (Ausbeute 42%) ... 

Dideoxy-3-C-methyl-4-(methylamino)-D-altrose (22) 3-Amino-2,3,6-trideoxy-3-C-methyl-L-/j/xo-hexose (23)... 

The addition reaction to branched glycoenopyranosides sometimes offers a stereospecific pathway to A-type, branched sugars. A stereospecific synthesis of the e valose (15) derivative (110) by cis-hy droxy lation of methyl 4-0-benzoyl-2,3,6-trideoxy-3-C-methyl-a-D-en/thro-hex-2-en-opyranoside (109), derived from 57a (R = Me), with osmium tetraoxide... 

Anthracyclines isolated from stieptomyces show a 2,3,6-trideoxy-3-amino-L-/yxo-configurated sugar oc-attached to the aglycon. Therefore, the first interest centered on the synthesis of aminodeoxy sugars in the l-lyxo series, e.g., daunosamine [46-50]. Several new glycosides were prepared [51] in order to evaluate structure-activity relationships. 

Brimacombe, J S, Rahman, K M M, Branched-chain sugars. Part 18. Syntheses of D-rubranitrose (2, 3,6-trideoxy-3-C-methyl-4-0-methyl-3-nitro-D-jiy/o-hexopyranose) and a derivative of D-kijanose (2,3,4,6-tetradeoxy-4-methoxycarbonylamino-3-methyl-3-nitro-a-D-ay/o-hexopyraose), J. Chem. Soc., Perkin. Trans. 1, 1073-1079, 1985, and previous references of this series. 

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