ISSN:
0570-0833
Keywords:
Cyclization
;
Dialdehydes
;
Nitromethane
;
Carbohydrates
;
Polyalcohols
;
Synthetic methods
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Condensation of nitromethane with suitable diadehydes in alkaline medium provides a general method of cyclization, in which the methyl group of the nitromethane is incorporated into the ring. This method leads to 5-, 6-, and 7-membered rings and is equally applicable to aliphatic, aromatic, and sugar dialdehydes. For example, glyoxal is converted into 1,4-dideoxy-1,4-dinitro-neo-inositol, and glutaraldehyde into trans-2-nitrocyclohexane-1,3-diol, while the corresponding cyclization of xylo-trihydroxyglutaraldehyde leads to deoxy-nitroinositols having the scyllo, myo-1, and muco-3 configurations.-In the case of aromatic dialdehydes, the cyclization is accompanied by elimination of water. Thus, phthalaldehyde, naphthalene-2,3-dicarboxaldehyde, and homophthalaldehyde yield, respectively, 2-nitroindenol, 2-nitrobenzindenol, and 2-nitronaphthalene. -Application of the method to sugar dialdehydes (aldehydic diglycol derivatives of monosaccharides formed by periodate oxidation) constitutes an excellent synthesis of 3-amino sugars, since 3-deoxy-3-nitropyranoses are formed smoothly on cyclization, and the corresponding 3-amino derivatives are obtained by hydrogenation. Thus, the reaction sequence: periodate oxidation → cyclization with nitromethane → hydrogenation, leads in the case of α-and β-D-pentosides to 3-amino-3-deoxy-D-and-L-pentosides, respectively, with ribo, xylo, and arabino configurations. α-D-hexosides give derivatives with gluco, manno, and galacto configurations. 3-Amino-3,6-dideoxyglucosides of the D-and L-series are obtained from 6-deoxy-D-or-L-hexosides, respectively, and 3-aminohexosans with gulo, ido, and altro configurations are obtained from 1,6-anhydro sugars. Cyclization of the dialdehydes obtained from sedoheptulose and methyl 4,6-O-ethylidene-α-D-glucoside by periodate oxidation, leads to 3-nitro and, after hydrogenation, to 3-amino derivatives of 3-deoxyheptopyranoses.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/anie.196402111
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