Derivatives Carbohydrates

—Separation of Fully Methylated Methyl a- and -D-Glycopyranoeides. (Xyl = xylose Ara = arabinose G = glucose Man = mannose Gal — galactose. Vertical dashes are at 10-min. intervals. Conditions column (6 ft. x i in.) of fully methylated 0-(2-hydroxyethyl)cellulose on Chromosorb (3 7 w/w) 190° 34 ml. of helium/rain. inlet pressure, 10 p.s.i. Thermal-conductivity detector.) 

The separation of fully methylated methyl glycosides has been extended 

RelerUion Volumes of Fully Methylated Disaccharides Relative to Oda-O-methylsucrose  

Retention Volumes of the Anomers of Methyl Tetra- and Tri-O-methyl-u-glucopyranosideii  

—Separation of Methyl Tri-O-methyl-a- and /S-D-GIucopyranosides. (Conditions column (10 ft. X J in.) of 20% by weight of hutanediol succinate polyester on firebrick 200° 77 ml. of helium/min.) 

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Glycosides are a large and very important class of carbohydrate derivatives character ized by the replacement of the anomeric hydroxyl group by some other substituent Gly cosides are termed O glycosides N glycosides S glycosides and so on according to the atom attached to the anomeric carbon... 

Section 28 2 Nucleosides are carbohydrate derivatives of pyrimidine and purine bases The most important nucleosides are derived from d ribose and 2 deoxy D ribose... 

Table 3. Carbohydrate Derivatives Used as Hplc Chiral Stationary Phases...

In the acid hydrolysis process (79—81), wood is treated with concentrated or dilute acid solution to produce a lignin-rich residue and a Hquor containing sugars, organic acids, furfural, and other chemicals. The process is adaptable to all species and all forms of wood waste. The Hquor can be concentrated to a molasses for animal feed (82), used as a substrate for fermentation to ethanol or yeast (82), or dehydrated to furfural and levulinic acid (83—86). Attempts have been made to obtain marketable products from the lignin residue (87) rather than using it as a fuel, but currently only carbohydrate-derived products appear practical. 

Glycoside (Section 25.13) A carbohydrate derivative in which the hydroxyl group at the anomeric position has been replaced by some other group. An O-glycoside is an ether of a carbohydrate in which the anomeric position bears an alkoxy group. 

Bu2SnO, benzene BnBr, DMF, heat, 80% yield. This method has also been used to protect selectively the anomeric hydroxyl in a carbohydrate derivative. The replacement of Bu2SnO with Bu2Sn(OMe)2 improves the process procedurally. The use of stannylene acetals for the regioselective manipulation of hydroxyl groups has been reviewed. ... 

Diethyl dithioacetal derivatives of carbohydrates are generally crystalline compounds which are easily prepared from sugars in the combined or free form. In contrast to the mass spectra of the carbohydrate derivatives discussed above, the mass spectra of diethyl dithioacetals allow direct determination of molecular weight from molecular-ion peaks of... 

Table II. Signs of Proton-Proton Constants of Carbohydrate Derivatives...

The widespread occurrence of long-range couplings in both furanose and pyranose derivatives explains why so many of the P.M.R. spectra of carbohydrate derivatives are apparently poorly resolved, even when the resolution of the spectrometer is above reproach. For example, the Hi resonance of the 1,6-anhydro-D-glucose derivative (12) is coupled to all of the other six ring protons. A further example of the line-broadening effect follows a consideration of the spectrum of 5,6-dideoxy-5,6-epithio-l,2-0-isopropylidene-/ -L-idofuranose for which the half-height... 

From a study (29) of the relative signs of various H, H coupling constants of carbohydrate derivatives it is evident that the couplings... 

It is evident from the above discussion that more-detailed studies of the P.M.R. spectra of carbohydrate derivatives will reveal an ever-increasing number of long-range couplings. Studies in this laboratory are directed towards the investigation of the occurrence of these couplings in the spectra of both furanose and pyranose derivatives. 

The word carbohydrate derives historically from the fact that glucose, the first simple carbohydrate to be obtained pure, has the molecular formula C6H,206 and was originally thought to be a "hydrate of carbon, C6(Tl20)6." This view was soon abandoned, but the name persisted. Today, the term carbohydrate is used to refer loosely to the broad class of polyhydroxvlated aldehydes and ketones commonly called sugars. Glucose, also known as dextrose in medical work, is the most familiar example. 

In addition to the common carbohydrates mentioned in previous sections, there are a variety of important carbohydrate-derived materials. Their structural resemblance to sugars is clear, but they aren t simple aldoses or ketoses. 

Addition to a,/(-Dialkoxy and Carbohydrate-Derived Carbonyl Compounds... 

Only moderate induced diastereoselectivity is achieved in the addition reactions of lithium enolates of the following a-silyloxy ketones43 and carbohydrate-derived ketones44, deproto-nated in each case at the methylene group in a regioselective manner to benzaldehyde. 

In general, chiral propanoates providing simple diastereoselectivity (in favor of yyn-aldols), combined with a reasonable degree of auxiliary-induced stereoselectivity, are rare. Numerous terpenoid- and carbohydrate-derived propionates do not display satisfactory syn selectivity60. Similarly, the titanium(IV) chloride promoted aldol addition of the following JV-metbylephe-drine derived silylketene acetal leads to the formation of the. mi-adduct in the moderate diastereomeric ratio of 78 22 (syn-adduct sum of the other stereoisomers)61. 

Carbohydrate-derived titanium cnolates also provide yvn-x-amino-/l-hydroxy esters of high diastcrcomeric and enantiomeric purity. For this purpose, the lithium enolate derived from ethyl (2,2,5,5-tetramcthyl-2,5-disilapyrrolidin-l-yl)acetate is first transmctalated with chloro(cy-clopentadienyl)bis(1,2 5,6-di-0-isopropylidene-a-D-glucofuranos-3-0-yl)titanium and subsequently reacted with aldehydes.. vj-n-a-Amino-/ -hydroxy esters are almost exclusively obtained via a predominant /te-side attack (synjanti 92 8 to 96 4 87-98% ee for the xvn-adducts)623-b. 

Carbohydrate-derived methyl ketone enolates show absolutely no induced diastereosclcctivity with respect to aldehydes see ... 

Starting from the appropriately substituted carbohydrates (e.g., II), 1,5-dialdehydcs are obtained by periodate oxidation. Subsequent double Henry reaction33 with nitromethane furnishes a variety of nitro-substituted carbohydrate derivatives. In most cases pure stereoisomers are obtained by crystallization of the reaction mixture3. 

A low stereoselection is also reported for an Ugi reaction which is the central step in the total synthesis of the antibiotic ( + )-furanomycin80. The carbohydrate-derived intermediate, formed from the following acetal and (+ )-a-methyIbenzylamine, reacts with benzoic acid and tert-butyl isocyanide to deliver the precursor 2 of the antibiotic and its diastcreomer 3 in equal amounts80. 

Ionophoresis of Some Carbohydrate Derivatives, A. B. Foster and M. Stacey, J. Applied Chem., 3 (1953) 19-21. 

The Oxidation of Some Carbohydrate Derivatives using Acetic Anhydride - Methyl Sulphoxide Mixtures and the Pfitzner-Moffat Reagent. Facile Synthesis of 3-Acetamido-3-deoxy-D-glucose and 3-Amino-3-deoxy-D-xylose, J. S. Brimacombe, J. G. H. Bryan, A. Husain, M. Stacey, and M. S. 

Hultin P. G., Earle M. A. and Sudharshan M. Synthetic Studies with Carbohydrate-Derived Chiral Auxiliaries Tetrahedron 1997 53 14823-14870 Keywords sugar-linked dienes, sugar-linked dienophiles... 

Wardell et al. studied the preparation, reactivities, and structures of C(carbohydrate)-Sn bonded mono-, or di-O-isopropylidene or di-O-benzylidene triphenylstannyl-carbohydrate derivatives by means of X-ray crystallography. 

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