Inosamine derivatives

Conversion to carbamates. Cyclic carbamates derived from sugars and related compounds have repeatedly been encountered, the first being an inosamine derivative, obtained by Curtius degradation of dihydroshikimic acid.82,83... 

Two inosamine derivatives containing axial amino groups were reported to give, on deamination, substitution products (in low or unspecified yield) with inversion158 and retention133 of configuration, respectively. No product analyses were reported. 

Kresze and co-workers utUized several of the adducts of a-chloroni-troso compounds and 5,6-disubstituted 1,3-cyclohexadienes in syntheses of some inosamine derivatives.For example, konduramin-Fl has been synthesized as depicted in Eq. (14). ... 

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). ... 

Odakura et al. used a high producer derivative of M. olivasterospora MK-70 (DSM 43868), strain KYI 1250, to isolate 25 mutants blocked in at least 10 different steps of biosynthesis, as juged from complementation patterns in cosynthesis or biotransformation studies using vcy/to-inosose, cy/to-inosamine... 

In all of the deaminations of inosamines just referred to, the substitution product was formed with inversion of configuration, but in no report was a product analysis given, and so, when a product was isolated in low yield, its significance is uncertain. In 1969, Angyal and Murdoch127 made a valuable contribution to these studies when they reported the results of detailed product-analysis for several inosamine deaminations. They confirmed that rearrangement is minimized by the use of O-acetyl derivatives, and their results for equatorial amines are summarized in Table II. The crystalline O-acetyl... 

The present review is to be regarded as a continuation of Fletcher s article1 the facts described therein will not be repeated here unless required for the understanding of recent developments. Because of the considerable expansion of cyclitol chemistry, it is not practicable to cover, as Fletcher did, all compounds of the cyclitol group. Only the inositols, the quercitols, and the inosamines, their derivatives, and some closely related compounds will be discussed the tetrahydroxycyclo-hexanes and -hexenes, and quinic and shikimic acids—on which subjects many important papers have appeared—are not reviewed here.3... 

Three inosamines were obtained in the course of efforts to synthesize myo-inositol by the nitro-sugar cyclization (see p. 142). However, the methods which have been the most productive of new inosamines are those which are well known as means of preparing amino sugars and aminopolyhydric alcohols, namely, reduction of imine derivatives of carbonyl compounds (in this case, inososes) and ammonolysis of halohydrins and epoxides. 

Tables II to X give the melting points and, where applicable, the optical rotations of the inositols, inososes, inosamines, and quercitols, and of all of their known O-substituted derivatives. Anhydroinositols, although not substitution products in the strict sense, are included, as are the carbonyl-functional derivatives of the inososes. Halogen- and nitro-substituted cyclitols, and the C-methyl-inositols and their derivatives, are not included most of these compounds are referred to in the text. The derivatives are arranged in the following order salts (inosamines) or functional derivatives (inososes), carboxylic esters, borates, nitrates, sulfonic esters, phosphates, glycosides, acetals (and Schiff bases), ethers (and IV-alkyl derivatives), and anhydrides.

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 rates of displacement of the sulphonate group by azide ion in DMF at 110 °C have been measured for a series of toluene-p-sulphonyl and p-bromo-benzenesulphonyl derivatives of 3-0-methyl-cA/ra-inositol and 4-0-methyl-tf//< -inositol in these compounds, the arylsulphonate group was located at position 4 (or 3), and the substituents at positions 1,2, 5, and 6 were isopropylidene, acetyl, methyl, and cyclic carbonate. All of the resulting azides (except the unreactive penta-O-methyl-c/j/ra derivative) could be converted into one of two inosamine penta-acetates, viz. lL-2-amino-2-deoxy-l-0-methyl-a//o-inositol and 1d-3-amino-3-deoxy-4-0-methyl-c/ /ra-inositol penta-acetates. The results were discussed in terms of currently held views on displacement reactions with carbohydrate and related sulphonates. 

Purified transamidinase preparations from S. griseus and 5. hikiniensis and a crude preparation from S. hluensis catalyzed, when incubated in the presence of L-arginine, the formation of phosphate esters of N-amidino-scyZ/o-inosamine, N-amidino-streptamine and N-amidino-2-deoxy-streptamine from phosphate esters of scy/Zo-inosamine, streptamine and 2-deoxy-streptamine, respectively. None of the enzyme preparations, however, catalyzed the addition of a second amidine group to these monoguanidinated molecules. It is not known whether this second guanidine group is derived via another transamidination reaction or by a different mechanism. 

Walker, M. S., and J. B. Walker Enzymatic studies on the biosynthesis of streptomycin Transamidination of inosamine and streptamine derivatives. J. Biol. Chem. 241, 1262 (1966). 

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