Levoglucosenone preparation

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

The following is the specific procedure for the preparation of levoglucosenone (2) by the pyrolysis of 5 g of cellulose (l).8 To a 50-mL round-bottom flask fitted with a vacuum distillation apparatus was added phosphoric acid (25 mg, 0.5 wt %), cellulose (5 g) and vegetable oil (15 g). The slurry was stirred for about 5 min under reduced pressure (20-30 mm Hg), and then heated by an appropriate heating mantle for 7 min to 270°C, as indicated by the internal thermometer. The reaction mixture began to turn black and water distillate appeared at about 140°C. Yellow distillate containing water and levoglucosenone (2) appeared on the flask wall around 270°C, and the temperature in the distillation head reached around 110-120°C. The reaction... 

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. 

Easily prepared from glycols, enones have been investigated as dienophiles. They react with butadiene under Lewis acid catalysis to form chiral cyclohexenes used in the synthesis of compactin analogs [353]. Levoglucosenone has been used in a Diels-Alder reaction with acetoxy-butadiene to construct a part of the indole alkaloid reserpine [354], and in synthetic studies toward tetrodotoxin [355]. Analogs of the anthracycline rhodomycinone have been similarly prepared [356]. [4 + 2]-Cycloaddition of the same enone with silyloxydiene allowed the creation of the fused ring system present in actinobolin [357]. 

Taniguchi, T, Ohnishi, H, Ogasawara, K, An expedient preparation of chiral building blocks having levoglucosenone chromophore a new enantiocontrolled route to (—)-p-multistriatin and (+)-exo-brevicomin, Chem. Commun., 1477-1478, 1996. 

Cerny M (1994) 1,6 2,3- and 1,6 3,4-Dianhy-dro-j6-D-hexopyranoses. Synthesis and preparative applications. In Witczak ZJ (ed) Frontiers in biomedicine and biotechnology. Levoglucosenone and levoglucosans, chemistry and applications. ATL Press, Mount Prospect, 2 121... 

Vogel and coworkers also developed entries into a variety of C-linked disaccharides and analogs based on the Oshima-Nozaki condensation of levoglucosenone and isolevoglu-cosenone with monosaccharide derived aldehydes [146]. For instance, a series of C-linked /3-(1 3)-glucopyranosides of 2- and 4-deoxy-D-hexoses were prepared by elaboration of the... 

The preparation and chemical properties of levoglucosenone as well as its use in the total synthesis of natural products have been reviewed, and the stereoselective reduction of 3-bromolevoglucosenone to l,6-anhydro-3-bromo-3,4-dideoxy-P-D-rAreo-hex-3-enopyranose 1 has been effected using zinc borohydride. The known lactone 2 has been converted into the aldosulose derivative 3, a degradation product from the ansamycin antibiotic (+)-trienomycin A. This confirmed that the fragment of the natural product was the enantiomer of 3. ... 

The previously reported alkene 335 (from L-glucose, vol. 28, p. 373) has now been elaborated to l2-e/ /-prostaglandin F2a- The C35-C43 subunit of dolastatin G (336) has been prepared from levoglucosenone. ... 

This section describes several new building blocks available from renewables, and how those building blocks can be converted by chemical processes into other materials. The contributions by Moens and Olson describe new uses for levulinic acid, an important renewable building block available inexpensively from cellulosic wastes (17), Kiely s paper on carbohydrate diacids describes approaches to selective glucose oxidation, the preparation of new polymers made from oxidized glucose, and where these materials might find use in the chemical industry. Witczak overviews uses of levoglucosenone, an... 

The Diels-Alder addition of dienes to levoglucosenone gives products 61 as intermediates useful for the preparation of functionalized cyclohexhane derivatives/ ... 

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... 

The preparation of branched-chain 4-eno-pyran-2-uloses derived from levoglucosenone is mentioned in Chapter 14. Studies on the addition of methanol to 2-C- and S-C-nitro-a- and P-D-cryt/iro-hex-2-enopyranosides as well as the preparation of C-1 glycosides by the addition of organometallic agents to 2,3-dihydro-4H-pyran-4-ones can be found in Chapter 3. 

The bis-branched-chain 3-pentulose (9) was formed in the formose reaction using thiamine HQ as catalyst under controlled conditions. The spiro-eponde (10), synthesized from levoglucosenone by the Corey procedure (NaH/McjSI/DMSO-THF), was used to prepare the branched derivatives (11) - (14). ... 

Various furanone chirons such as (22)-(24), and their C-5 epimers, have been prepared in optically-pure form from the dibromide (25) and its C-5 epimer these in turn are easily accessible from L-ascorbic and D-isoascorbic acids. 2 Baeyer-Villiger oxidation of levoglucosenone leads to the formation of the... 

Conventional Grignard reaction of levoglucosenone followed by hydroxylation has been used to prepare 1,6-anhydro-2-C-tetradecyl altropyranose. 

The lactone (6), prepared by a stereocontrolled aldol condensation followed by resolution of the enantiomers, has been converted into methyl cladinoside (7). Some branched 5-amino-2,5,6-trideoxy-hexose derivatives (eg (8)) have been prepared from a l,5-dideo3ty-pent 2-ulose derivative. Treatment of levoglucosenone with a basic excess of nitromethane has afforded products (9) and (10), whereas... 

Chapters 15 and 16 the preparation of N-containing enones is mentioned in Chapter 9 the use of levoglucosenone in the preparation of altrose is reported in Chapter 2 and the preparation of some enone-C-glycosides can be found in Chapter 3. 

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