Inosamines synthesis

Only one example is available of the use of a preformed true anhydro-inositol for inosamine synthesis (+)-l, 2-anhydro-3,4 5,6-di-0-isopropyl-idene-aZZo-inositol (CXXVII) yields (-j-)-neo-inosamine-l (CXXVIII) and Zero-inosamine-3 (/ewo-inosamine-o, CXXIX) on ammonolysis and hydrolysis.214 However, the epoxide CXXX and its pentaacetate CXXX (see below) have been treated with ammonia and with a variety of primary and... 

The synthesis of inosamines from bromodeoxyinositols has been achieved by way of displacement reactions with sodium azide in boiling, aqueous 2-methoxyethanol or N,N-dimethylformamide.163... 

The final step in the synthesis—replacement of the amino group in XI by a hydroxyl group—was carried out by Posternak28 by treatment with nitrous acid. Inversion occurred, giving a 10-15% yield of myo-inositol the other products of the reaction could not be identified. A much better yield (71 %) was achieved by the nitrous acid deamination of the penta-acetate ester of XI, rather than by deamination of the free inosamine.30,31 This method has been utilized30,31 for the preparation of myo-inositol- -C14 from nitromethane-C 14. 

Kresze and cowoikers have used nitroso Diels-Alder reactions in synthesis of a variety of inosamines and related compounds. One example of this work is the synthesis of conduramine-Fl (92) as shown in equation (34). In this case, diene (91) reacted with a-chloro nitroso cyclohexane to afford adduct (91) as the only product. Just why this stereoisomer was formed is not obvious. Compound (91) could be converted to the conduramine in a few steps. 

Aminocyclitols are oxidized if they have axial hydroxyl groups, and here, again, the axial hydroxyl groups are attacked. The sensitive amino group must be protected during the oxidation—conveniently, by means of a ben-zyloxycarbonyl group. He3ms and Paulsen i catalytically oxidized iV-ben-zyloxycarbonyl-DL-myo-inosamine-4 (74r-75) to iV-benzyloxycarbonyl-DL-2-keto-mj/o-inosamine-4 (76-77) in the presence of Adams catalyst this constituted the first synthesis of a cyclic amino ketone. This reaction is an important step in the streptamine syntheas devised by these authors. 

Synthesis of Inosamine and Inosadiamine Derivatives from Inositol Bromohydrins, M. L. Wolfrom, Jack Radell, R. M. Husband, and G. E. McCasland,/. Amer. Chem. Soc., 79, 160-164 (1957). 

The Suami and Ogawa group has been particularly active in the field of carbocyclic polyols. The main line of their interest was confined to the synthesis of aminocyclitols, constituents of aminoglycoside antibiotics and their analogs. Besides, inosamines and aminocyclopentanepolyols obtained in their laboratory were utilized as substrates in synthesis of nucleoside analogs. A... 

G. Kresze, W. Dittel, and H. Melzer, Polyhydroxyamines via Diels-Alder synthesis with nitroso compounds. VI. Synthesis of inosamine derivatives, Liebigs Ann. Chem., 224 (1981),... 

The di(benzyloxy)cyclohexene (9) mentioned above has also been used to synthesize racemic deoxyinosamine, deoxyinosadiamine, and inosamine derivatives via the unsaturated inosamine derivatives (16) and (17) Scheme 5 illustrates the basic sequences that were applied to both isomers. The same group has similarly prepared racemic amino-cyclitols from 3-benzyloxycyclohexene, and 3-methoxycyclohexene was used for a synthesis of the peracety-late d DL - 2,5 - diamino -2,3,5- trideoxy-4 -0-5-N- dimethyl - ch iro - inositol (18). Base-catalysed cyclization of the substituted diones (19) gave the corresponding cyclitols (20), which were then used to prepare other 2,l -substituted cyclitols including mono- and di-amino-cyclitols, e.g., (21). ... 

The regio- and stereo-selective synthesis of inosamines and inosadiamines utilizing Diels-Alder reactions with nitroso compounds has been reviewed. 

The incorporation of an inosamine into the complete synthesis of hygromycin A, the structure determination of mannostatins A and B, and the synthesis of carbocyclic nucleoside antibiotics are mentioned in Chapter 19, and the synthesis of phospholipids incorporating pyranosyl-myo-inositol units is referred to in Chapter 3. Carbocyclic nucleosides are covered in Chapter 20. 

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