Cyclitol derivatives

Simple analogs of an aminoglycoside antibiotic, 2,6-dideoxy-4-0- (671) and -5-0-(2,3-dideoxy-2-fluoro-o -D-r/Z>o-hexopyranosyl)streptamine (672) were prepared by coupling of tri-O-acetyl-2-fluoro-D-glucal (666) with cyclitol derivatives 668 or 667 (through 669 and 670) as shown. 

One of the efficient method for constructing carbohydrates is the Diels-Alder reaction, which gives a variety of important synthetic intermediates for the synthesis of cyclitol derivatives. We therefore were interested in the development of asymmetric Diels-Alder reaction by the use of chiral titanium reagents. 

Acyclic carbohydrates with one alkyl chain are either derived from cyclitols or aldonic acids. Acyclic cyclitol derivatives 3 (X=0, S, NH, N(CH3), NHCO, N(CH3)C0 R=Q-Ci6 sug=Glc-ol, Man-ol) form thermotropic liquid crystals... 

Isogai A, Sakuda S, Nakayama J, Watanabe S, Suzuki S (1987) Isolation and structural elucidation of a new cyclitol derivative, streptol, as a plant growth regulator. Agric Biol Chem 51 2277... 

The Ferrier II reaction, a carbocyciization reaction, is of widespread use as a tool for the conversion of glycosides into cyclitols [ 183,184,185]. Newer examples for the utilization of the reaction conducted under catalytic conditions [186,187] have appeared in the recent literature. Compound 221 is converted into cyclohexanone 222 on the way to (—)-mesembranol [188] (O Scheme 48). Compound 223 is transformed to the enone 224, the precursor of several new cyclitol derivatives [189,190,191]. 

The cyclitol derivatives of streptomycin (streptidine and strepturea), although not strictly glycosyl ureides, are mentioned here since they are close relatives of the series. ... 

Grosheintz and Fischer synthesized the 6-deoxy-6-nitro derivatives of D-glucose and L-idose by treating l,2-0-isopropylidene-a-D-a i/lo-pento-dialdo-l,4-furanose with nitromethane, and employed these sugars for cyclization to cyclitol derivatives. These reactions and their importance in cyclitol chemistry have already been reviewed in this Series. - ... 

The original purpose was to cyclize this compound to a cyclitol derivative by treatment with potassium in xylene. However, a crystalline diene derivative (115) was formed which, after hydrolysis of the methylene groups, gave crystalline l,6-dideoxy-D-(/ireo-2,5-hexodiulose (116). It showed no indications of the presence of a double bond and reduced Fehling solution in the cold. The location of the two keto groups at C-2 and C-5 in this compound and in the diulose (118), obtained later, was proved by ozonization of their parent diene compound (115) to yield D-threaric acid. The compound (116) showed no mutarotation and was converted into a crystalline bis[(p-nitrophenyl)hydrazone] and di-(p-nitrobenzoate). 

A crystal structural analysis of mwco-inositol is referred to in Chapter 21. iV-(2-chloroethyl)-iV-nitrosoureido derivatives of cyclopentane- and cyclohexane-tetrols are mentioned in Chapter 18. Unsaturated glycosylated cyclitol derivatives are referred to in Chapter 12. 

Other Cyclitol Derivatives. - The distribution of products in the gas-phase acid-induced ring-opening with methanol, as well as condensed phase meth-anolysis, of cyclohexene oxides e.g. 220) bearing remote O-functionality has been studied. Products and ratios varied widely depending on the reaction phase. 

Several polycyclic cyclitol derivatives have been reported. The decalinic compound 221 was synthesized from 3,4,6-tri-O-acetyl-D-glucal. As shown in Scheme 33, intramolecular Diels-Alder cycloaddition of the triene set up a tricyclic hex-5-enopyranoside derivative which underwent Ferrier rearrangent with mercuric sulfate and aqueous sulfuric acid to afford 221. Exhaustive osmylation of... 

Othman AA, AI-Masudi NA, Timari US (1978) A new route to the synthesis of cyclitol derivatives. J Antibiot 31 1007-1012... 

D-Quercitol (73) is common in members of the genus Quercus, oaks, of the family Fagaceae. This cyclitol derivative is known from at least nine other families. D-Pinitol (63) is known from six families of gymnosperms, in which it is widespread, but it is also known from a number of angio-sperms. 

Several glycosylations of cyclitol derivatives are referred to in Chapter 18. 

Figure 33 Biogenesis of some of the hexose-, pentose-, and cyclitol-derived components in ACAGAs from 6-IC I-D-giucose (according to Ref. 8). The labeling patterns in neomycin and vali-damycin measured by nuclear magnetic resonance (NMR) prove that all units are built up preferentially from C, (circled C atoms), C. or C, units (thick lines) rearranged by transketolase-and transaldolase-catalyzed reactions in passages through the pentosephosphate cycle. The paiiem in Cal products is hypothetical. The positions derived from the C6 of D-glucose are marked by a star.

The presence of a cyclitol derivative in the antibiotic streptomycin is very interesting. (For more details, see Chapter X.) This derivative, strept-amine, has been shown to be a diaminodideoxy-sc /Ho-inositol of the following structure 1S3) ... 

The synthesis of the carba di- and tri-saccharides 103 has been described. and the preparation of carba-disaccharide 104 by a similar process to that reported earlier (Vol. 25, p. 214, ref. 95) has appeared. For the preparation of glycosides of cyclitol derivatives see also Chapter 3. Carbocyclic analogues of GDP fucose have been made as potential inhibitors of fucosyl transferases. ... 

The cyclitol derivatives (27) and (28) (see Chapter 18) were found to adopt in solution the "inverted" conformations shown, with the benzyloxymethyl groups axially disposed. ... 

A new digalactosyl cyclitol from the seed balls of sugar beet has been characterized as 0,-ef-D-Gal p(l- 6)-0- -D-Gal p(l- 2)-1-D-chiro-A series of cyclitol derivatives (23)-(25) have been... 

D-Quinic acid has been converted into the cyclitol derivative (71) a precursor in a synthesis of daunomycinone. ... 

Roush and co-workers have effectively applied the Peterson olefmation conditions to synthesise cyclitol derivatives as intermediates in their approach towards the conduritol natural products. Starting from common precursors 97, both acidic and basic conditions were employed to give the desired alkenes 98/100 in excellent yields removal of the protecting groups then furnished the natural products 99/101. 

As is customary, this section contains reference to antibiotics comprising amino-sugars glycosidically linked to various aglycons - not just cyclitol derivatives. The title is sometimes used for this latter group exclusively. 

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