Cyclitols and Derivatives

Reviews have appeared on the synthesis of inositols, carba sugars, conduritols and amino conduritols utilizing the non-carbohydrate sources of benzene cis-diols, quinic acid and Vogel s naked sugar methodology. Other reviews on the preparation of cyclophellitol and ep/-cyclophellitol from glycals and the use of D-glyceraldehyde as a chiral precursor in Diels-Alder and 1,3-dipolar cycloaddition approaches to carbocyclic derivatives have also been reported. 

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T. Hudlicky and M. Cebulak, Cyclitols and Derivatives, A Handbook of Physical, Spectral and Synthetic Data, VCH, New York, 1993. 

Oxidative interconversion of cyclitols and derivatives into acyclic, di-carboxylic acids has been widely used for structural elucidation in this series. Early applications of the procedure helped determination of the constitution of shikimic and quinic acids for example, cleavage of the 1,2,3-triol grouping of methyl dihydroshikimate (35) produced a dialdehyde (36), which was oxidized with bromine water to the (known) degradation end product, tricarballylic acid (37). This approach to structural problems has proved particularly successful for determining the configuration of glycosides and related compounds. 

Alditols and Cyclitols and Derivatives Thereof - cis-Inositol monohydrate,2,4,6-tri-0-benzyl-/wyo-inositol 1,3,5-tris-dibenzylphosphate, 3,4,5,6-tetra- 0-benzyl-1,2- 0-cyclohexylidene-myo-inositol, ( )-1,4-di- O-benzoyl-2,3-0-isopropylidene-myo-inositol and ( )-l,4-di-0-benzoyl-5,6-0-isopropylidene-m> o-inositol, wyo-inositol derivatives 61 and 62, (D)-l-0-allyl-3,6-di-0-benzyl-2-0-[(-)-camphanoyl]-4,5-0-isopropylidene-sc> //o-inositol 63, and fluoro-inositol derivative M (also Chapter 18, and section 1 for IR). ... 

Cyclitols and Derivatives. - A review on the application of the Pd(II)-catalysed Ferrier (II) carbocyclization in the synthesis of p-glucosidase inhibitors, cyclophellitol, all the diastereoisomers of inositol, and D-myo-inositol phosphates has been published. ... 

Alditols, Cyclitols and Derivatives Thereof,- Meso-D- /ycero-L-a/tro-heptitol and its monohydratc and hcptaacetate, meso-D- /ycero-L-ido-heptitol and its heptaacetate, i,3,4,5-tetra-0-benzyl-p-D-fhictopyranosyl cyanide, 34 le cyclopropane fused carbocyclic nucleoside analogue 63, neplanocin intermediatB 64,the cyclopentane 65, l,3,S,7-tetraoxadecalins 66 and 67... 

Many other cyclitols and derived compounds are themselves achiral, but are capable of giving rise to chiral derivatives when suitably substituted. One of the best studied examples is deoxystreptamine, which occurs as substitution products in antibiotics of the Kananycin-neomycin type. See p. C3 and also M. Hichens and K. L. Rinehart, J. Amer. Chem. Soc., 1963,85, 1547. 

Alditols, Cyclitols and Derivatives Thereof. - 2,5 3,4-Dianhydro-D-altritol, 2,5-aohydro-3,4-0-(l,2-ethanediyl)-D mannitol, pentaerythritol tetraacetate, ribitol tetraacetate, xylitol tetraacetate, D-arabinitol tetraacetate, D, L-arabinitol tetraacetate, 2,4 3,5-di-0-isopropylidene-D-mannitol, 2 hexa-O-acetyl-D-mannitol, allitol hexaacetate, D-mannitol hexaacetate, D, L-mannitol hexaacetate, D-iditol hexaacetate, D, L-iditol hexaacetate, D, L-glucitol hexaacetate, D, L-altritol hexaacetate, L-galacto-D-galacto-decitol (which is C2-symmetric), 5 6-0-benzyl-2,3-0-[(S)-caniphanylidene]-l,4,5-tris-0-pivaloyl-D-myo-inositol, 6D-3,6-di-0-benzyl-l-0-[(S)-camphanyl]-2-deoxy-2,2-difluoro-4,5-0-isopropylidene- y< -inositol, cyclopentane 28. ... 

Alditols. Cyclitols and Derivatives Thereof.- 1,2,3,4,5-Penta-Q-acetyl-l-C-[(5 ,6S)-5-exo-nitro-bicvclo[2.2.1]hept-2-en-6-endo-yl]-D-manno-pentitol and its 5-endo-6-exo-isomer. and the (RS)- -diastereoisomers of l,6-dichloro-l,6-dideoxy-D-mannitol 2,4 3,5-bis-Q-(H-piperidyIphosphate). "... 

Alditols. Cyclitols and Derivatives Thereof.- 4-(D-arabino-Tetritol-l-yl)-4-imidazolin-2-ylideneammonium chloride, (4R, 5R)-4-(D-arabino-l 2.3.4-tetraacet03 butyl)-l,2-dimethyl-5-nitro-l-anthraquinone derivative (20), l-(3,5-dimethyl-3-nitro-l-pyrazolm-4-yl)-penta-Q-... 

Alditols, Cyclitols and Derivatives Thereof. - The structural determination of gualamycin 47 has been assisted by X-ray analysis of the aglycon methyl ester hydrochloride. 

Aldolases catalyze asymmetric aldol reactions via either Schiff base formation (type I aldolase) or activation by Zn2+ (type II aldolase) (Figure 1.16). The most common natural donors of aldoalses are dihydroxyacetone phosphate (DHAP), pyruvate/phosphoenolpyruvate (PEP), acetaldehyde and glycine (Figure 1.17) [71], When acetaldehyde is used as the donor, 2-deoxyribose-5-phosphate aldolases (DERAs) are able to catalyze a sequential aldol reaction to form 2,4-didexoyhexoses [72,73]. Aldolases have been used to synthesize a variety of carbohydrates and derivatives, such as azasugars, cyclitols and densely functionalized chiral linear or cyclic molecules [74,75]. 

Remarkable selectivity has been observed in the oxidation of molecules containing several secondary hydroxyl groups, such as al-dopentopyranosides, 6-deoxyaldohexopyranosides, cyclitols, and various anhydro derivatives. As indicated previously, attack usually occurs at relatively hindered hydroxyl groups. When aqueous solutions of benzyl /3-D-arabinopyranoside, benzyl jS-D-ribopyranoside,... 

In the last twenty years, nitro sugars became powerful chemical tools on account of their usefulness for the construction of carbon-carbon bonds prior to the transformation of the nitro group into a variety of other chemical functionalities. As a result, a diverse range of funcionalized carbohydrates and other derivatives as carbasugars, cyclitols and heterocycles have been prepared. 

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.

Aldol-type cyclization of dialdehydes with nitroalkanes is a valuatde syndietic loute to amino sugars, amino cyclitols and nucleosides of amino sugars. Recently, die cyclization of die di- and tetra- de-hydes derived from sucrose (15) with nitroalkanes has appeared. It is notewordiy that the oxidadve cleavage of sucrose with LTA affords the dialdehyde selectively (Scheme 8). ... 

For more information see Fludlicky, T., and Cebulak, M., Cyclitols and Their Derivatives (New York VCH, 1993). 

The naked sugars of the first generation (319, 320, 321, (+)-322, (—)-322) are useful chirons for preparing all kinds of rare sugars derivatives [180] and analogs such as C-linked disaccharides [181]. They have been converted into conduritols, cyclitols and carbahexose derivatives [174,182]. The bicyclic ketones can also be converted into their enoxysilanes and then cleaved by ozonolysis. Depending on the workup conditions, 2,5-anhydrohexaldaric acid or 2,5-anhydrohexonic acid derivatives can be readily prepared in both enantiomerically pure forms [183]. 

Aminoglycosides Containing Cyclitol, Monoaminocyclitol, Diamino-cyclitol, and Related Derivatives... 

The usual solvents are deuterium oxide for free cyclitols, and cliloro-form-d for their nonpolar derivatives, such as acetates. The use of methyl sulfoxide may be advantageous. When necessary, samples of one milligram or less may be examined, using special micro-cells or micro-tubes... 

Figure 5. Some branched cycloses, cyclitols and alpha, beta-unsaturated cyclic ketones derived from xylaric acid some acyclic c> /o (8 - 9) and ribo (10) ring precurors.

Also of interest in the phytochemical field are the favourable results obtain from the GC analysis of cyclitols and polyols as both their TMS and TFA derivatives [226] silylation being achieved with BSA/TMCS (19 1) with heating at 75 °C for 20 min. Interfering monosaccharides can be converted to oximes or dithioacetals prior to silylation (see Chapters 6 and 7). 

Interest continues in glycosylated derivatives of cyclitols and related compounds (see also Chapter 18). Thioglycoside technology was used to synthesize compound 45 vriiich is an analogue of the chromophore of neocarzinostatin. Various and cAiro- inositol... 

In view of the wide distribution of the cyclohexanehexols (called inositols or cyclitols) and the importance of one in particular (myo-inositol) to certain bacteria, plants, and perhaps even to warm-blooded animals, the naturally occurring and synthetic compounds of this carbocyclic class have received considerable study. Naturally occurring members include four inositols, monomethyl ethers, a dimethyl ether, monodeoxy derivatives, one dideoxy derivative, a methyl homolog, and deoxy carboxylic acids. Five inositols and many other synthetic members, including ketones (cycloses or inososes), are known. 

Syntheses of amino-derivatives of branched-chain sugars, cyclitols and nucleosides are covered in Chapters 14, 18 and 20, respectively. 

Cyclitols are widely distributed in nature, albeit never in large quantities. The patterns of distribution and the biochemistry of cyclitols and their conjugates and derivatives are so interesting and important that their occurrence (23, 119, 140, 151), isolation (151), determination (23, 151), taxonomic significance (137), chemistry (23, 25, 151), biochemistry (24, 118-120, 151) and physiological importance (24,151) have been frequently reviewed and discussed. Metabolic relationships between isomeric inositols and their methyl ethers, the amounts found in some plant tissue, and the fluctuations encountered suggest a storage function (see 119). 

Cyclitols and symmetrical acyclic polyols have been desymmetrized by fonnation of dispoke adducts such as myo-inositol derivative 7. ... 

Various cyclitols (and acyclic polyols) have been desynunetrized by formation of dispoke intermediates. (See for example, Vol. 28, p. 237, ref. 115). L-Chiro-inositol can be converted to the silyl derivative 67 in which the trans-diol units are protected on reaction with l,3-dichloro-l,l,3,3-tetraisopropylidisiloxane (TipsQ). Compound 67 was further converted into conduritol B epoxide and its thioepoxide analogue. The conversion of some tetra-O-substituted myo-inosi-tols into adipic dialdehyde derivatives is mentioned in Chapter IS. 

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