From levoglucosenone synthesis

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. 

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

Mori, M, Chuman, T, Kato, K, Mori, K, A stereoselective synthesis of natural (45,65,75)-serricomin, the sex pheromone of cigaret beetle, from levoglucosenone, Tetrahedron Lett., 23, 4593-4596, 1982. 

Witczak, Z J, Synthesis of C-glycosyl compounds and other natural-products from levoglucosenone. Pure Appl. Chem., 66, 2189-2192, 1994. 

Isobe, M, Fukami, N, Nishikawa, T, Goto, T, Synthesis of chiral cyclohexanes from levoglucosenone and its application to an indole alkaloid reserpine, Heterocydes, 25, 521-532, 1987. 

Blattner R, Furneaux RH, Mason JM, Tyler PC (1994) Synthesis of the herbicide 1,6-anhydro-4-0-benzyl-3-deoxy-2-0-methyl-/i-D-ribohex-opyranose and analogues from Levoglucosenone and Levoglucosan. In Witczak ZJ (ed) Levoglucosenone and Levoglucosans Chemistry and Application. ATL Press Science Publishers, Mt. Prospect, IL, p 43... 

Some interesting examples of levoglucosenone s application in the synthesis of natural products and rare carbohydrates have been reported (58-81). Indeed, levoglucosenone has been used in the synthesis of (+)-multistriatin (58,72-73), Prelog-Djerassi lactonic acid (58,59) md (-)-a//o-yohimbane (61) The synthesis of indole alkaloid reserpine (61), and serricomin (58), as well as tetrodotoxin (53,62) were also reported from levoglucosenone or its functionalized derivatives and was reviewed earlier by us (1). 

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... 

The isomeric 2-deoxy-1,4-lactones 8 and 9 have been synthesized in a multi-step procedure from levoglucosenone, while the branched lactones 10 and 11 have been prepared by radical addition [C6H13I or Ph(CH2)3l, Bu3SnH, AIBN] to an unsaturated aldonic acid ester.The lactone 12, an intermediate in the synthesis of pseurotin A, has been prepared from D-glyceraldehyde in a multi-step procedure. Thermally-induced cleavage of nitrate ester 13 [derived from... 

Levoglucosenone has been employed as a substrate for successful enzymatic syntheses. For example, recently Allais and coworkers described [10] a very effective chemoenzymatic synthesis of optically pure (S)-Y-hydroxymethyl-a,p-butenolide (23), using a two-step sequence involving a hpase-mediated Baeyer-Villiger oxidation and an acid hydrolysis from levoglucosenone. Another valuable product these authors transformed levoglucosenone into is (S)-Y-hydroxymethyl-Y-butyrolactone (22). Both products in an enantiomerically pure form have been used as chiral synthons in a variety of total syntheses. The discussed compounds are shown on Scheme 11.6. 

SCHEME lf.7 Elegant synthesis of allal from levoglucosenone. 

SCHEME 11.8 Synthesis of thio and amino substituted isolevoglucosenone derivatives from levoglucosenone. 

Levoglucosenone and its functionalized analogue have been synthesized from furan by employing either enzymatic resolution or asymmetric synthesis. The potential of the latter as a chiral building block has been demonstrated by synthesis of all eight hexose diastereomers and some other natural products. 

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]. 

The Yohimbe alkaloids such as alloyohimbane (1) and the antihypertensive drug reserpine constitute attractive goals for synthetic chemists. Syntheses of Yohimbe alkaloids from noncarbohydrates have been reported. " Synthesis of 1 from cellulose has also been achieved (Scheme 1). Pyrolysis of cellulose gave the levoglucosenone (l,6-anhydro-3,4-dideoxy- 3-D-glycero-hex-3-enopyrano-2-ulose, 2), which underwent Diels-Alder cycloaddition with... 

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. ... 

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