Chiral carbohydrate building block

Chiral Carbohydrate Building Blocks with a New Perspective Revisited... 

Levoglucosenone (1), an attractive chiral carbohydrate building block, is conveniently produced by the pyrolysis of cellulose composed materials. Despite the disadvantages of its low yield and the amount of solid cellulosic material necessary for pyrolysis, the efficiency and the economy of the pyrolysis process makes it an effective method. In addition, pyrolysis reduces the amount of waste cellulosic material, which is beneficial to the environment. 

Two syntheses and one formal synthesis of (+)-preussin have been reported using sugars as chiral pool building blocks. In these syntheses parts of the sugar backbone have been implemented into the preussin skeleton. All four pyrrolidine carbon atoms stem from the carbohydrate. As a consequence, the two carbon-nitrogen bonds (N/C-2 and N/C-5) of the pyrrolidine ring... 

As alternatives to nucleophilic additions to C6 or C5 aldehydes, olefinations of the same compounds offer a repertoire of solutions to chain extensions or to the coupling of two carbohydrate building blocks. As shown in the above section, chain extensions at C6 are often followed by the introduction of new functional groups and thus new chiral centers. In this regard, olefins obtained via Wittig-type reactions are excellent starting compounds. 

A nice and convergent approach to both compounds makes use of RCM to form the 5-membered building block 71, which mimics the carbohydrate part of the nucleosides. The necessary diene precursor 69 is readily assembled via Evans aldol chemistry. RCM then affords the ring in almost quantitative yield (69->70), leaving the chiral centers and the free hydroxyl group intact. Removal of the chiral auxiliary by reductive cleavage, attachment of the base by means of jt-allylpalladium chemistry, and a final deprotection step complete these highly efficient syntheses [46]. 

Several enzymatic procedures have been developed for the synthesis of carbohydrates from acyclic precursors. Aldolases appear to be useful catalysts for the construction of sugars through asymmeteric C-C bond formation. 2-deoxy-KDO, 2-deoxy-2-fluoro-KDO, 9-0-acetyl sialic acid and several unusual sugars were prepared by a combined chemical and enzymatic approach. Alcohol dehydrogenases and lipases have been used in the preparation of chiral furans, hydroxyaldehydes, and glycerol acetonide which are useful as building blocks in carbohydrate synthesis. 

Enzymatic reduction of carbonyl compounds and enzymatic enantioselective transformation of racemic or meso alcohols (25,43.) are two methodologies that have proven to be beneficial in the preparation of optically active hydroxyl compounds, key chiral building blocks used in carbohydrate and natural product syntheses (44-45. Our interest in this area is to develop enzymatic routes to optically active glycerol and furan derivatives, and hydroxyaldehydes. 

Carbohydrates are configurationally stable, easily available in enantiopure forms from the chiral pool, and they show a high density of chiral information per molecular unit. Their polyfunctionality and structural diversity fadhtate their tailor-made modification, derivatization, and structural optimization for a broad spectrum of synthetic applications. While derivatives of various saccharides have already been utilized as versatile starting materials and building blocks for chiral auxiliaries, ligands, and reagents [330] their obvious role as precursors for the... 

It is worth pointing out that, besides o-sorbitol 19 and D-mannitol 36, other low-molecular weight building blocks have been already obtained on the ton-scale from low cost or waste polymeric carbohydrates (starch, cellulose, hemicellulose, chitin) [80, 81]. Most of these compounds are densely functionalized enantiopure molecules that can be easily converted into high-value added products, including chiral ionic liquids. Therefore, further studies are required to develop other synthetic approaches to environmentally sustainable ionic liquids based on renewable raw materials. 

Building blocks derived from microbial transformations are usually employed as the key units of fluorinated analogs of appropriate natural products or synthetic biologically active materials [42-45]. Among such useful compounds, trifluoromethylated carbohydrates constitute one of the most interesting fields for intensive study. Novel and efficient routes to access a variety of chiral... 

The direct homologation technique was then extended to the synthesis of various uncommon carbohydrate structures. Thus, higher sugars of the L-series were obtained Starting from 2,3-0-isopropylidene-4-O-benzyl-L-threose (43) [39c] (Scheme 13), and the amino tetrose 47 and pentose 48 were prepared from the a-amino aldehyde 46 derived from L-serine [46a] (Scheme 14). These amino sugars were used as chiral building blocks for the... 

Additionally, the environmental issue of utilizing waste cellulosic material and waste biomass products should be considered as an alternative green chemistry application to the production of many value added products. The combinatorial utilization of carbohydrate scaffolds based on chiral building block functionalization will also constitute attractive and relatively cheap starting materials. This rich selection of potential approaches, combined with further developments of new procedures and modem reagents, creates an enormous opportunity for the field to be at the frontier for many years to come. 

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