Levoglucosenone

Levoglucosenone as an optically active starting material 97YGK1074. 

Anhydro-3,4-dideoxy-p-D-g/ycero-hex 3-enopyranos-2-ulose (trivial name levoglucosenone)... 

Levoglucosenone, a cellulose-derived a,(3-unsaturated ketone, is an interesting material because it is both chiral and contains an activated double bond. This compound has been used... 

A variety of important synthetic reactions can he promoted by electrogenerated bases (EGB). The Michael addition and alkylation of compounds with activated hydrogen atoms are two examples in which using EGB has been very successful. The electrochemical method is very successful for functionalization of levoglucosenone as shown in Scheme 4.28.198... 

A new strategy has been developed for the construction of pentacyclic skeletons of alkaloids such as (-)-alloyohimbane [(-)-365] starting from optically active carbohydrate levoglucosenone (397). 

A salient example regarding a Michael addition of nitronates to a,(5-unsaturated carbonyl compounds is the stereoselective addition of glucosyl nitromethane 93 to levoglucosenone (94) in the presence of tetramethylguanidine (TMG) (Scheme 30).70... 

Instead of a triflate, the electrophile on the glycosyl acceptor can be an a,(3-unsaturated carbonyl group. This is the case reported in Fig. 25, in which a stereoselective Michael addition of the 1-thiosugar 56 to the a,(3-conjugated system of levoglucosenone 57, generated after deprotection a couple of L-fucopyranosyl-4-thiodisaccharides 61 and 62 presenting inhibitory activity on a-L-fucosidase.54... 

Levoglucosenone, a bicyclic dihydropyranone, is accessible even more directly by vacuum pyrolysis of waste paper." Although the yield attainable is relatively low—levoglucosan is also formed, the amount depending on the exact conditions... 

Scheme 2.6)—relatively large amounts can be amassed quickly levoglucosenone has been used for the synthesis of a diverse variety of natural products in enantio-pure form." ... 

Witczak, Z. J. Chhabra, R. Chen, H. Xie, X. Q., Thiosugars.2. A novel approach to thiodisaccharides - The synthesis of 3-deoxy-4-thiocellobiose from levoglucosenone. 

Griffin A, Newcombe NJ, Gallagher T (1994) In Witczak ZJ (ed) Levoglucosenone and levoglucosans, chap 3, ATL Press, Mount Prospect... 

The synthesis started with levoglucosenone 4, available by the pyrolysis of cellulose, e.g. old newspapers. Bromination-dehydrobromination gave the enantiomerically-pure Diels-Alder dienophile 5, which was combined with isoprene to give predominantly the crystalline adduct 1. Hydrolysis and acetylation led to 6, which was carried on to the geometrically-defined allylic alcohol 7 via reduction with Zn-Cu couple. Overman rearrangement of 7 proceeded with high facial control, to give 8. 

A. C. Forsyth, R. M. Paton, and I. Watt, Highly selective base-catalyzed additions of nitro-methane to levoglucosenone, Tetrahedron Leu. 30 993 (1989). 

R. Blattner and D. M. Page, Radical addition to levoglucosenone, synthesis of anhydrosugar herbicide analogues, J. Carbohydr. Chem. 132 21 (1994). 

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. 

K. Matsumoto, T. Ebata, K. Koseki, H. Kawakami, and H. Matsushita, Synthesis of D-allosan from levoglucosenone, Heterocycles, 32 (1991) 2225-2240. 

Figure 9. Thermal analysis of levoglucosenone samples (a) neat, (b) +5% zinc chloride, (c) +5% diammonium phosphate, and (d) +5% diphenyl phosphate (D.t.a., differential thermal analysis T.g., thermo gravimetry D.t.g., derivative of thermogravimetry)...

The chiral bicyclic enones, levoglucosenone, isolevoglucosenone, and new functionalized L-arabinose enone possess excellent reactivity and functionality. Their properties mid application as convenient precursors in the synthesis of many attractive templates or intermediates of complex natural products are reviewed. These compounds are attracting increasing interest due to their structural rigidity and ability for stereoselective functionalization without protection, deprotection sequences necessary in many synthetic organic methodologies. 

Examples of these convenient chiral building blocks reviewed in this chapter include levoglucosenone, isolevoglucosenone and L-arabinose derivatives. 

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