33647-85-7Relevant academic research and scientific papers
Manipulating the enone moiety of levoglucosenone: 1,3-Transposition reactions including ones leading to isolevoglucosenone
Ma, Xinghua,Liu, Xin,Yates, Patrick,Raverty, Warwick,Banwell, Martin G.,Ma, Chenxi,Willis, Anthony C.,Carr, Paul D.
, p. 5000 - 5011 (2018/06/20)
The manipulation of the enone moiety associated with the biomass-derived, homochiral and now abundant compound levoglucosenone (1) is described. While the trichloroacetimidates derived from the allylic alcohols 3 and 4 failed to engage in Overman-type rea
Diastereoselective Weitz-Scheffer epoxidation of levoglucosenone for the synthesis of isolevoglucosenone and derivatives
Ledingham, Edward T.,Greatrex, Ben W.
, p. 6107 - 6115 (2018/09/14)
High-yielding epoxidation conditions for the cellulose pyrolysis product (?)-levoglucosenone (LGO) and 3-aryl derivatives of LGO have been developed. The reaction of LGO with hydrogen peroxide/base is known to give a Baeyer-Villiger reaction, however, it was found that the reactions of LGO or derivatives with tert-butylhydroperoxide/base affords solely epoxides through the Weitz-Scheffer reaction. A critical parameter in the successful isolation of the epoxide from LGO was to avoid all contact with water or alcohols during the reaction and workup. The epoxide products were reacted under Wharton conditions affording allylic alcohols and subsequent oxidation led to isolevoglucosenone or 3-arylisolevoglucosenone derivatives. Previously unreported reactions on isolevoglucosenone were then investigated.
The conversion of levoglucosenone into isolevoglucosenone
Ma, Xinghua,Anderson, Natasha,White, Lorenzo V.,Bae, Song,Raverty, Warwick,Willis, Anthony C.,Banwell, Martin G.
, p. 593 - 599 (2015/04/27)
Levoglucosenone (1), a compound that will soon be available in tonne quantities through the pyrolysis of acid-treated lignocellulosic biomass, has been converted into isolevoglucosenone (2) using Wharton rearrangement chemistry. Treatment of compound 1 with alkaline hydrogen peroxide gave the γ-lactones 5 and 6 rather than the required epoxy-ketones 3 and/or 4. However, the latter pair of compounds could be obtained by an initial Luche reduction of compound 1, electrophilic epoxidation of the resulting allylic alcohol 8 and oxidation of the product oxiranes 9 and 10. Independent treatment of compounds 3 and 4 with hydrazine then acetic acid followed by oxidation of the ensuing allylic alcohols finally afforded isolevoglucosenone (2). Details of the single-crystal X-ray analyses of epoxy-alcohols 9 and 10 are reported.
Synthesis of α-bromoisolevoglucosenone and its cyclopenta annulation
Biktagirov,Faizullina,Salikhov,Safarov,Valeev
, p. 1317 - 1322 (2015/01/08)
4,4-Dimethyl-3-nitro-10,11-dioxatricyclo[6.2.1.02,6]undec-5-en-7-one possessing a bicyclic iridoid skeleton was synthesized in two steps from isolevoglucosenone which was obtained in turn from levoglucosenone through 4-benzyloxy-2-tosyloxy deri
Total synthesis of (+)-ambruticin S
Berberich, Stephen M.,Cherney, Robert J.,Colucci, John,Courillon, Christine,Geraci, Leo S.,Kirkland, Thomas A.,Marx, Matthew A.,Schneider, Matthias F.,Martin, Stephen F.
, p. 6819 - 6832 (2007/10/03)
A convergent total synthesis of the novel antifungal agent ambruticin S (1) has been completed from the assembly of intermediates 18, 33 and 52 that served as the respective A-, B-, and C-ring precursors. The first generation approach to a potential A-ring intermediate eventuated in the synthesis of 9a via a route that featured oxidation of the dihydroxy furan 2 and elaboration of the dihydropyranone 3 derived therefrom. Although 9a served as a precursor of 31E to complete a formal synthesis of 1, there were several inefficiencies associated with the preparation of 9a. A more expedient and efficient route to an A-ring subunit was devised that commenced with the carbohydrate-derived bisacetonide aldehyde 10 and produced 18 in five steps and 46% overall yield. The synthesis of the cyclopropyl sulfone 33 was initiated with the enantioselective cyclopropanation of 19 catalyzed by Rh 2[5(S)-MEPY]4. Ring opening of the resultant lactone 20 followed by a series of refunctionalizations gave 33 in a total of seven steps and 46% yield from 19. Coupling of the A- and B-ring precursors 18 and 33 was then achieved via a modified Julia coupling followed by deprotection and oxidation to furnish the key intermediate 35. The dihydropyran core of the C-ring subunit precursor 49 was formed from the ring closing metathesis of the diene 48, which was prepared in three steps from the known epoxide 45, followed by oxidation. A chelation-controlled addition to the methyl ketone 49 set the stage for a stereoselective [2,3]-Wittig rearrangement that delivered the alcohol 51 that was then transformed in two steps to the sulfone 52. A traditional Julia coupling of 52 and 35 proceeded with excellent stereoselectivity, and subsequent removal of the various protecting groups gave ambruticin S (1). The longest linear sequence was 13 steps and proceeded in 4. 3% overall yield.
A new approach to isolevoglucosenone via the 2,3-sigmatropic rearrangement of an allylic selenide
Witczak, Zbigniew J.,Kaplon, Peter,Kolodziej, Mark
, p. 143 - 148 (2007/10/03)
A convenient method is described for the synthesis of isolevoglucosenone 5, via allylic selenide 3, and its rearrangement to allylic alcohol 4, followed by oxidation with manganese oxide. Isolevoglucosenone 5, is produced in 62% overall yield.
Chemoselective elaboration of O-linked glycopeptide mimetics by alkylation of 3-thioGalNAc
Marcaurelle,Bertozzi
, p. 1587 - 1595 (2007/10/03)
A critical branch point in mucin-type oligosaccharides is the β1 → 3 glycosidic linkage to the core α-N-acetylgalactosamine (GalNAc) residue. We report here a strategy for the synthesis of O-linked glycopeptide analogues that replaces this linkage with a
Thio-sugars. Part 5: From D-glucal to 3-deoxy-(1→2)-2-S-thiodisaccharides through isolevoglucosenone-a simple approach
Witczak, Zbigniew J.,Chen, Hong,Kaplon, Peter
, p. 519 - 532 (2007/10/03)
A new synthesis of isolevoglucosenone and its stereoselective functionalization into 3-deoxy-(1-2)-2-S-thiodisaccharides is described. The base-catalyzed conjugate addition of 1-thiosugars to isolevoglucosenone followed by the reduction of the C-4 keto function constitute a new two-step general approach to these classes of biologically important thio-sugars. Copyright (C) 2000 Elsevier Science Ltd.
Lipase-mediated preparation of enantiopure isolevoglucosenone
Kadota,ElAzab,Taniguchi,Ogasawara
, p. 1372 - 1374 (2007/10/03)
A route to enantiopure isolevoglucosenone, a regioisomer of levoglucosenone and a potential chiral building block, has been developed by employing lipase-mediated kinetic resolution as the key step.
Cycloaddition of cyclopentadiene to 3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-erythro-hex-3-enofuranose. Synthesis and representative chemistry of 1,6-anhydro-2,3-dideoxy-β-D-glycero-hex-2-enopyran-4-ulose ("isolevoglucosenone")
Horton, Derek,Roski, James P.,Norris, Peter
, p. 3783 - 3793 (2007/10/03)
Treatment of D-glucose-derived alkene 4 with cyclopentadiene in the presence of a Lewis acid results in the formation of cycloaddition products 8-11. Evidence is presented to show that these 1,6-anhydro sugar-cyclopentadiene adducts do not arise from rearrangement of 4 to isolevoglucosenone (5) followed by cycloaddition but are the result of Lewis acid-catalyzed rearrangement of alkene 4 to acyclic dienophile 12 followed by addition of cyclopentadiene. Major cycloadduct 8 has been utilized as a source of the enantiomerically pure carbocycles 14-25 by manipulation of the alkene and ketone functions and cleavage of the 1,6-anhydro bridge. In the absence of diene, alkene 4 undergoes rearrangement to enone 5 in 32% yield. Reaction of 5 with several dienes results only in the formation of "bottom-face" adducts 10, 11, 28, and 29, and conjugate addition of either HN3 or Me3COOH is found to be completely stereoselective to afford 30 and 31, respectively. Subsequent manipulation of azide 30 leads to precursors of several naturally occurring 2-amino-2,3-dideoxy sugars.
