Levoglucosenone conversion

In the area of waste utilization, Fred s program on the heat content, gasification, and carbonization of forest fuel is now recognized as a major step in our understanding of forest fires. The acid-catalyzed pyrolysis of cellulosic waste to afford l,6-anhydro-3,4-dideoxy-)3-D-g/ycero-hex-3-enopyranos-2-ulose ( levoglucosenone ) pointed the way to another method of chemical conversion of cellulosic wastes similar to cat-cracking in the petrochemical industry. 

A Convenient Procedure for the Preparation of Levoglucosenone and Its Conversion to Novel Chiral Derivatives... 

Preliminary report of this procedure "Convenient procedure for the preparation of levoglucosenone from cellulose and the conversion of levoglucosenone to novel chiral derivatives", paper by W. S. Trahanovsky, C. Wang, J. M. Ochoada, and S. Chang as part of the Symposium on Chemistry of Renewable Fuels and Chemicals, at the 217th National Meeting of the American Chemical Society, Anaheim, California, March 1999. Abstract and Preprint FUEL 35. 

As noted above, one difficulty which prevents versatile use of levoglucosenone 1 is its sturdy internal acetal functionality. We, therefore, designed12 a levoglucosenone carrying a handle on an appropriate position such as 6-alkoxymethyllevoglucosenone 20 so as to cleave the internal acetal functionality without difficulty. If 20 is available, its acetal linkage may be cleaved after conversion into a halomethyl derivative 21 to give a hemiacetal 22 under reductive conditions (Scheme 6). 

Additionally, convenient conversion of levoglucosenone into isomeric isolevoglucosenone (82) (Scheme 16) utilizes the more of the potential of this molecule. 

A comprehensive review has appeared this year on the conversion of carbohydrate derivatives to functionalized cyclopentanes and cyclohexanes, and another review has described the synthesis of natural products from carbohydrates using the Perrier rearrangement.2 (+)-Methyldihydroepijasmonate 2 has been prepared from levoglucosenone (Scheme 1). The n-pentyl group was introduced by stereoselective cuprate addition, and the carbocyciic ring was formed via 5-exo-trig alkylation of the enolate derived from 1 (Scheme 1)2... 

Oxirans. - The synthesis of l,2-anhydro-3,4-di-0-benzyl-6-deoxy-a-D-glucopyranose and its conformational analysis have been reported. A range of epoxides have been prepared by base treatment of bromohydrins, which were made by reaction of hydrogen bromide with aldonolactones. A one-pot conversion of vicinal diols into epoxides employs halohydrin ester intermediates generated from cyclic orthoacetates and either acetyl bromide or trimethylsilyl chloride. Levoglucosenone has been transformed into l,6 3,4-dianhydro-p-D-talopyranose by way of a trn/w-iodo-acetoxylation of the alkene moiety... 

Efficient procedures for the conversion of levoglucosenone to rare sugars, e.g., D-altrose, D-allose, 4-deoxy-o-mannose, have been devised. Hydrolytic opening of the L-sorbopyranose-derived epoxide 12 with nucleophilic attack at C-4 was the key-step in the transformation of L-sorbose to L-fructose, which requires inversion of configuration at C-3 and C-4. The formation of D-tagatose from d-... 

Other anhydrides. - l,6-Anhydro-2-deoxy-2-iodo-P-D-glucopyranose has been prepared directly from D-glucal (Scheme 3). The conversion of levoglucosenone into 4-deoxy-D-(yxo-hexose is... 

This methodology was initially applied to a synthesis of (—)-alloyohimbane (82) (Scheme 3.13) (29). Readily available levoglucosenone (75), a product of cellulose pyrolysis, was the starting material. Diels-Alder reaction of 75 with 1,3-butadiene afforded adduct 76 which underwent Wolff-Kishner elimination and subsequent acylation to provide the bicyclic enol ether 77. Hydrolysis followed by oxidation and saponification afforded hydroxymethyl lactone 78 which was then condensed with tryptamine to yield the amide diol 79. Periodate cleavage of the diol was followed by conversion to chloride 80 which was cyclized to afford lactam 81. Subsequent Bischler-Napieralski cyclization followed by hydrogenation of the olefin moiety afforded the target ( )-alloyohimbane (82). 

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