No description available.

No description available.

No description available.

The metabolism of carbohydrates in guayule is a subject which has not been considered with respect to its role in cis-polyisoprene synthesis, It has been suggested that acetate or sucrose act as the distal, and isopentenylpyrophosphate as the immediate precursor of the isoprenoid biosynthetic pathway. Application of radioactive precursors to the leaves of guayule plants in Winter and Summer showed that the fate of the carbohydrate depends on the chemical structure of the carbohydrate and the time of application. [[14]C] Sucrose was incorporated into the acetone (resin) fraction during the Summer and petroleum ether (rubber) fraction during the Winter. The amount of radioactivity that was translocated in Winter and Summer was similar. The loss of leaves during Winter reduced the area for photosynthesis, while the loss of carbon from the leaves during Summer, probably due to photorespiration, decreased the amount of available photosynthates. These two phenomena did not disadvantage the plant as far as the allocation of carbon was concerned. No plant components were acting as sinks during the Winter. The pith of the crown area incorporated the most radioactivity in Summer. [[14]C] Fructose was more readily translocated than [[14]C] sucrose during a 12 hour experiment. When fructose was applied and plants were left for 48 hours, more radioactivity was translocated to the stems and roots during the Summer. The [[14]C] from fructose was incorporated into the acetone (resins) rather than the petroleum ether (rubber) fraction in Winter therefore apparently having a different fate to [[14]C] sucrose. The principal reserve carbohydrates in guayule are fructans. Two types of fructans were detected and are referred to as water-soluble or ethanol-soluble fructans. The ethanol-soluble fructan polymers apparently played an active role in metabolism of guayule and showed cyclic patterns of accumulation. The water-soluble fructans seem to be true reserve carbohydrates, depolymerizing when the carbon supply decreased at the end of Winter, and the demand for carbon increased at the inception of bud break. Fructans provide carbon for budbreak and exposure of plants to longer days and higher temperatures did not seem to alter this role. It is proposed that fructans are providing carbon for budbreak and renewed growth and are utilized for flowering when required. Starch production occurs during the warmer months in the leaves and young stems. Starch is synthesized from the immediate photosynthetic supply and it is this source of carbon which is utilized for the synthesis of cis-polyisoprene (rubber). Sucrose in the cytosol is sequestered for cis-polyisoprene synthesis while fructose, which can enter the plastid, is providing carbon for the synthesis of isoprenoids. Compartmentation of resin and rubber production ensures that the supply of carbon is adequate for both processes. As cis-polyisoprene synthesis occurs at a time when the plant is not disadvantaged by insufficient carbon , induction of rubber transferase enzymes would not depend on excess substrate, but would use a more reliable cue like temperature or daylength. Any attempt therefore to increase the carbon supply in guayule during the winter months would not necessarily lead to partitioning into cis-polyisoprene, but may be stored as fructan to ensure that, at bud break, the plant has an adequate and utilizable carbon supply. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1991.

Sulfated carbohydrates play key roles in a wide range of biological processes such as blood clotting, viral entry into cells, amyloidogenesis, neurite outgrowth, tumor growth and metastasis. However, their synthesis still remains a considerable challenge. A general approach to the synthesis of sulfated carbohydrates was examined in which sulfate group is incorporated at the beginning of the syntheses as a protected sulfodiester. Towards this end, a series of sulfuryl imidazolium salts (SIS), a new class of sulfating agents, was prepared and examined as reagents for incorporating 2,2,2-trichloroethyl-protected sulfate esters into monosaccharides. The SIS that contained a 1,2-dimethylimidazolium moiety proved to be a superior sulfating agent compared to SIS bearing no alkyl groups or bulkier alkyl groups on the imidazolium ring. Difficult O- and N- sulfations that required prolonged reaction times and a large excess of the SIS bearing a 1-methylimidazolium group were achieved in high yield and in less time when employing less than half the 1,2-dimethylimidazolium derivative. Efforts were then made to apply the sulfate protecting group strategy to the total synthesis of a class of chondroitin sulfate glycosaminoglycans. These studies revealed some of the limitations of the sulfate protecting group approach to the synthesis of sulfated oligosaccharides. Studies on the selective introduction and isomerization of the carbobenzyloxy protecting group into 2,3-diols of 4,6-O-benzylidene galactose derivatives are also reported.

Sulfated polysaccharides are widespread in nature. These compounds are implicated in a wide variety of important biological processes such as blood clotting, cell adhesion, and cell–cell communication. However, detailed characterization of their specific biological roles has proved to be very challenging. One reason for this is that the synthesis of even relatively small sulfated oligosaccharides still remains a considerable challenge. A general approach to the synthesis of sulfated carbohydrates was examined in which the sulfate group is incorporated at the beginning of the syntheses as a protected sulfodiester. Towards this end, a series of modified sulfuryl imidazolium salts were prepared and examined as reagents for incorporating 2,2,2-trichloroethyl-protected sulfate esters into monosaccharides.. A more efficient sulfating agent was obtained by incorporating a methyl group at the 2-position of the imidazolium ring. O-Sulfations that required prolonged reaction times and a large excess of the original sulfuryl imidazolium salt (SIS) which bears no alkyl groups on the imidazolium ring, were more readily achieved using the new reagent. Direct regioselective incorporation of TCE-protected sulfates into monosaccharides was achieved using the new imidazolium salt. We have also shown that the new SIS can also be used for the direct disulfation of monosaccharides and that trisulfated monosaccharides can also be prepared from the disulfated compounds. SIS’s bearing the TFE and phenyl groups, were readily prepared. In most instances, both TFE- and phenyl protected sulfated carbohydrates were easily prepared in good yields using SIS’s. Deprotection of the TFE group from secondary sulfates in carbohydrates and aryl sulfates was achieved in excellent yields using NaN3 in DMF. We applied the sulfate protecting group strategy towards the total synthesis of the tetrasaccharide portion of a disulfated glycosphingolipid called SB1a. Efficient routes were developed for the construction of the left- and right-hand protected disaccharide portions of the SB1a tetrasaccharide.

No description available.

No description available.

This thesis describes the synthesis of three novel seven carbon bicyclic mimics of α-L-fucose, and of two new pyrrolidine amino sugars. 2,7-Anhydro- l-deoxy-β-L-gulo-heptulopyranose and l,2,7-trideoxy-2,7-imino-β- L-gulo-heptulopyranose were both synthesised from L-gulono-l,4-lactone. The addition of one equivalent of methyllithium to the diacetonide of L-gulono-1,4- lactone gave a keto-sugar, l-deoxy-3,4;6,7-di-0-isopropylidene-β-L-gulo- heptulofuranose. The anomeric configuration of this compound was determined by equilibrium nOe measurements. Hydrolysis in aqueous trifluoroacetic acid caused simultaneous deprotection, isomerisation and dehydration to yield 2,7-anhydro-l-deoxy-β-L-guloheptulopyranose, a highly stable, rigid bicyclic system. The structure of the bicyclic system was confirmed by X-ray crystallographic studies on a crystalline derivative. The introduction of nitrogen at C-6 of L-gulono-l,4-lactone was achieved via the azide displacement of the known bromide, 6-bromo-6-deoxy-2,3-0- isopropylidene-L-gulono-l,4-lactone. Protection of the C-5 hydroxyl group as its silyl ether was followed by the addition of one equivalent of methyllithium to the carbonyl group to give a keto-sugar, 7-azido-6-(0-tert-butyldimethylsilyl-l,7- dideoxy-3,4-0-isopropylidene-β-L-gulo-heptulofuranose. Removal of the protecting groups followed by reduction of the azide functionality gave the bicyclic hemiaminal, l,2,7-trideoxy-2,7-imino-β-L-gulo-heptulopyranose, a stable but hygroscopic solid. A third bicyclic system, 2,7-anhydro-l,2,6-trideoxy-2,6-imino-β-L-gulo- heptulopyranose, was synthesised from diacetone-D-mannose via the known ketosugar, 6-azido-7-0-tert-butyldimethylsilyl-l,6-dideoxy-3,4-0-isopropylidene-β- L-gulo-heptulofuranose. Removal of the protecting groups from this keto-sugar, followed by reduction of the azide functionality, gave the target system. Analysis of the NMR spectra showed that this existed as an equilibrium mixture of the closed, bicyclic hemiaminal form and the monocyclic imine form, with the bicyclic form predominating in all solvents investigated. The sodium borohydride reduction of l-deoxy-3,4;6,7-di-0-isopropylidene-β-L-gulo-heptulofuranose gave a single product, the heptitol 7-deoxy-l,2;4,5-di-0-isopropylidene- L-glycero-D-gluco-heptitol. This was converted into two novel pyrrolidine amino sugars, l,2,5-trideoxy-2,5-imino-L-glycero-L-allo-heplitol and l,2,5-trideoxy-2,5-imino-L-allitol. The two free hydroxyl groups in the heptitol were converted into leaving groups and one was then displaced selectively with sodium azide. Reduction of the azide functionality gave an amine which cyclised onto the remaining leaving group to form the pyrrolidine framework. Complete deprotection of this product gave l,2,5-trideoxy-2,5-imino-L-glycero-L-allo- heptitol, the structure of which was confirmed by X-ray crystallographic studies on a crystalline derivative. Removal of the primary acetonide from the cyclisation product and subsequent periodate cleavage gave an aldehyde which was then reduced to an alcohol. Deprotection then gave the second pyrrolidine amino sugar l,2,5-trideoxy-2,5-imino-L-allitol. The effect of all five target compounds on eleven human liver glycosidase enzymes was investigated, and these results are also reported.

No description available.