The synthesis and manipulation of certain Diels–Alder adducts of levoglucosenone and iso-levoglucosenone
Brett Pollard
A , Xin Liu A , Luke A. Connal A , Martin G. Banwell B * and Michael G. Gardiner A
A
B
Abstract
Diels–Alder cycloaddition reactions between the biomass-derived platform molecule levoglucosenone (2) and various cyclic dienes such as α-terpinene produced a range of adducts, including compound 28. Manipulation of these adducts then afforded a series of derivatives. So, for example, reductions of the associated carbonyl groups delivered the corresponding alcohols including compound 29 and on reaction of these with diethylaminosulfur trifluoride rearranged fluorination products such as tetracycle 30 were obtained. An analogous suite of compounds was obtained by manipulation of the Diels–Alder adducts derived from reacting the same dienes with iso-levoglucosenone that was itself obtained through simple manipulation of levoglucosenone. Our earlier studies suggest that various of these derivatives could be used in the production, via ring-opening metathesis polymerisation (ROMP), of new bio-based polymers.
Keywords: chiral pool, cycloaddition, enones, fluorination, heterocycles, levoglucosenone, iso-levoglucosenone, polymers.
References
1 Comba MB, Tsai Y, Sarotti AM, Mangione MI, Suárez AG, Spanevello RA. Levoglucosenone and its new applications: valorization of cellulose residues. Eur J Org Chem 2018; 2018: 590-604.
| Crossref | Google Scholar |
2 Banwell MG, Pollard B, Liu X, Connal LA. Exploiting nature’s most abundant polymers: developing new pathways for the conversion of cellulose, hemicellulose, lignin and chitin into platform molecules (and Beyond). Chem Asian J 2021; 16: 604-620.
| Crossref | Google Scholar | PubMed |
3 Allais F. Total syntheses and production pathways of levoglucosenone, a highly valuable chiral chemical platform for the chemical industry. Curr Opin Green Sustain Chem 2023; 40: 100744.
| Crossref | Google Scholar |
4 Camp JE, Greatrex BW. Levoglucosenone: bio-based platform for drug discovery. Front Chem 2022; 10: 902239.
| Crossref | Google Scholar | PubMed |
5 Klepp J, Bousfield T, Cummins H, Legendre SVA-M, Camp JE, Greatrex BW. Oxa-Michael-initiated cascade reactions of levoglucosenone. Beilstein J Org Chem 2022; 18: 1457-1462.
| Crossref | Google Scholar | PubMed |
6 Nikahd M, Mikusek J, Yu L-J, Coote ML, Banwell MG, Ma C, Gardiner MG. Exploiting chitin as a source of biologically fixed nitrogen: formation and full characterization of small-molecule hetero- and carbocyclic pyrolysis products. J Org Chem 2020; 85: 4583-4593.
| Crossref | Google Scholar | PubMed |
7 Nikahd M, Mikusek J, Banwell MG, Yu L-J, Coote ML, Gardiner MG. Further, small-molecule pyrolysis products derived from chitin. Aust J Chem 2020; 73: 1187-1196.
| Crossref | Google Scholar |
8 Ma X, Anderson N, White LV, Bae S, Raverty W, Willis AC, Banwell MG. The conversion of levoglucosenone into isolevoglucosenone. Aust J Chem 2015; 68: 593-599.
| Crossref | Google Scholar |
9 Ma X, Liu X, Yates P, Raverty W, Banwell MG, Ma C, Willis AC, Carr PD. Manipulating the enone moiety of levoglucosenone: 1,3-Transposition reactions including ones leading to isolevoglucosenone. Tetrahedron 2018; 74: 5000-5011.
| Crossref | Google Scholar |
10 Banwell MG, Liu X, Connal LA, Gardiner MG. Synthesis of functionally and stereochemically diverse polymers via ring-opening metathesis polymerization of derivatives of the biomass-derived platform molecule levoglucosenone produced at industrial scale. Macromolecules 2020; 53: 5308-5314.
| Crossref | Google Scholar |
11 Liu X, Carr P, Gardiner MG, Banwell MG, Elbanna AH, Khalil ZG, Capon RJ. Levoglucosenone and its pseudoenantiomer iso-Levoglucosenone as scaffolds for drug discovery and development. ACS Omega 2020; 5: 13926-13939.
| Crossref | Google Scholar | PubMed |
12 Liu X, Pollard B, Banwell MG, Yu L-J, Coote ML, Gardiner. MG, van Vugt-Lussenburg BMA, van der Burg B, Grasset FL, Campillo E, Sherwood J, Byrne FP, Farmer TJ. Simple and modestly scalable synthesis of iso-Cyrene from levoglucosenone and its comparison to the bio-derived and polar aprotic solvent Cyrene®. Aust J Chem 2022; 75: 331-344.
| Crossref | Google Scholar |
13 Diot-Néant F, Mouterde L, Fadlallah S, Miller SA, Allais F. Sustainable synthesis and polycondensation of levoglucosenone-cyrene-based bicyclic diol monomer: access to renewable polyesters. ChemSusChem 2020; 13: 2613-2620.
| Crossref | Google Scholar | PubMed |
14 Diot-Néant F, Mouterde LMM, Couvreur J, Brunois F, Miller SA, Allais F. Green synthesis of 2-deoxy-D-ribonolactone from cellulose-derived levoglucosenone (LGO): A promising monomer for novel bio-based polyesters. Eur Polym J 2021; 159: 110745.
| Crossref | Google Scholar |
15 Diot-Néant F, Mouterde LMM, Veith C, Couvreur J, Miller SA, Allais F. Sustainable one-pot synthesis and polycondensation of a levoglucosenone-derived cyclic acetal diol. ACS Sustainable Chem Eng 2022; 10: 10132-10143.
| Crossref | Google Scholar |
16 Fadlallah S, Peru AAM, Flourat AL, Allais F. A straightforward access to functionalizable polymers through ring-opening metathesis polymerization of levoglucosenone-derived monomers. Eur Polym J 2020; 138: 109980.
| Crossref | Google Scholar |
17 Fadlallah S, Flourat AL, Mouterde LMM, Annatelli M, Peru AAM, Gallos A, Aricò F, Allais F. Sustainable hyperbranched functional materials via green polymerization of readily accessible levoglucosenone-derived monomers. Macromol Rapid Commun 2021; 42: 2100284.
| Crossref | Google Scholar |
18 Fadlallah S, Kayishaer A, Annatelli M, Mouterde LMM, Peru AAM, Aricò F, Allais F. Fully renewable photocrosslinkable polycarbonates from cellulose-derived monomers. Green Chem 2022; 24: 2871-2881.
| Crossref | Google Scholar |
19 Fadlallah S, Carboué Q, Mouterde LMM, Kayishaer A, Werghi Y, Peru AMM, Lopez M, Allais F. Synthesis and enzymatic degradation of sustainable levoglucosenone-derived copolyesters with renewable citronellol side chains. Polymers 2022; 14: 2082.
| Crossref | Google Scholar | PubMed |
20 Kayishaer A, Fadlallah S, Mouterde LMM, Peru AAM, Werghi Y, Brunois F, Carboué Q, Lopez M, Allais F. Unprecedented biodegradable cellulose-derived polyesters with pendant citronellol moieties: from monomer synthesis to enzymatic degradation. Molecules 2021; 26: 7672.
| Crossref | Google Scholar | PubMed |
21 Debsharma T, Schmidt B, Laschewsky A, Schlaad H. Ring-opening metathesis polymerization of unsaturated carbohydrate derivatives: levoglucosenyl alkyl ethers. Macromolecules 2021; 54: 2720-2728.
| Crossref | Google Scholar |
22 Warne CM, Fadlallah S, Whitwood AC, Sherwood J, Mouterde LMM, Allais F, Guebitz GM, McElroy CR, Pellis A. Levoglucosenone-derived synthesis of bio-based solvents and polyesters. Green Chem Lett Rev 2023; 16: 2154573.
| Crossref | Google Scholar |
23 Middleton WJ. New fluorinating reagents. Dialkylaminosulfur fluorides. J Org Chem 1975; 40: 574-578.
| Crossref | Google Scholar |
24 Oberdorfer F, Haeckel R, Lauer G. Reactions of 2-hydroxy-6,8-dioxabicyclo[3.2.1]oct-3-ene with diethylaminosulfur trifluoride and with halogens. Facile synthesis of 1,6-anhydrohalohexopyranoses. Synthesis 1998; 1998: 201-206.
| Crossref | Google Scholar |
25 Karban J, Císařová I, Strašák T, Šťastná LČ, Sýkora J. Skeletal rearrangements resulting from reactions of 1,6:2,3- and 1,6:3,4-dianhydro-β-D-hexopyranoses with diethylaminosulphur trifluoride. Org Biomol Chem 2012; 10: 394-403.
| Crossref | Google Scholar | PubMed |
26 Horník Š, Červenková Šťastná L, Cuřínová P, Sýkora J, Káňová K, Hrstka R, Císařová I, Dračínský M, Karban J. Synthesis and in vitro cytotoxicity of acetylated 3-fluoro, 4-fluoro and 3,4-difluoro analogs of D-glucosamine and D-galactosamine. Beilstein J Org Chem 2016; 12: 750-759.
| Crossref | Google Scholar | PubMed |
27 Hierso J-C. Indirect nonbonded nuclear spin–spin coupling: a guide for the recognition and understanding of “through-space” NMR J constants in small organic, organometallic, and coordination compounds. Chem Rev 2014; 114: 4838-4867.
| Crossref | Google Scholar | PubMed |
28 Zurita MA, Avila A, Spanevello RA, Suárez AG, Sarotti AM. Montmorillonite K-10 promoted synthesis of chiral dioxa-caged compounds derived from levoglucosenone. Carbohydr Res 2015; 402: 67-70.
| Crossref | Google Scholar | PubMed |
29 Horton D, Roski JP, Norris P. 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”). J Org Chem 1996; 61: 3783-3793.
| Crossref | Google Scholar | PubMed |
30 Ward DD, Shafizadeh F. Cycloaddition “4 + 2” reactions of levoglucosenone. Carbohydr Res 1981; 95: 155-176.
| Crossref | Google Scholar |
31 Sarotti AM, Spanevello RA, Suárez AG. Assessing the halogen effect in Diels–Alder reactions involving chiral α-halo enones. A combined experimental and DFT computational approach. Tetrahedron Lett 2011; 52: 4145-4148.
| Crossref | Google Scholar |
32 Davydova AN, Pershin AA, Sharipov BT, Valeev FA. Synthesis of chiral 2,3-cis-fused butan-4-olides from levoglucosenone–1,3-diene Diels–Alder adducts. Mendeleev Commun 2015; 25: 271-272.
| Crossref | Google Scholar |
33 Galimova YS, Khalilova YA, Sharipov BT, Spirikhin LV, Rameev SR, Safiullin RL, Valeev FA. Reaction of levoglucosenone with (±)-α-terpineol and its acetate. Russ J Org Chem 2014; 50: 1848-1850.
| Crossref | Google Scholar |
34 Essig MG, Stevenson TT, Shafizadeh F, Stenkamp RE, Jensen LH. (1S)-(1α,4α,5β,5aβ,6β,8β,9β,9aβ)-Octahydro-5,8-dihydroxy-1,4-epoxy-6,9-methano-3-benzoxepin-7(2H)-one (a levoglucosenone derivative). The product of a 1,4-hydride shift. J Org Chem 1984; 49: 3652-3656.
| Crossref | Google Scholar |
35 Plietker B. New oxidative pathways for the synthesis of α-hydroxy ketones—the α-hydroxylation and ketohydroxylation. Tetrahedron Asymmetry 2005; 16: 3453-3459.
| Crossref | Google Scholar |
36 Still WC, Kahn M, Mitra A. Rapid chromatographic technique for preparative separations with moderate resolution. J Org Chem 1978; 43: 2923-2925.
| Crossref | Google Scholar |
37 Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ. Safe and convenient procedure for solvent purification. Organometallics 1996; 15: 1518-1520.
| Crossref | Google Scholar |
38 Bhaté P, Horton D. Stereoselective synthesis of functionalized carbocycles by cycloaddition to levoglucosenone. Carbohydr Res 1983; 122: 189-199.
| Crossref | Google Scholar |
39 Sarotti AM, Spanevello RA, Duhayon C, Tuchagues J-P, Suárez AG. Exploring structural effects of levoglucosenone derived chiral auxiliaries in asymmetric Diels–Alder cycloadditions. Tetrahedron 2007; 63: 241-251.
| Crossref | Google Scholar |
40 Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H. OLEX2: a complete structure solution, refinement and analysis program. J Appl Crystallogr 2009; 42: 339-341.
| Crossref | Google Scholar |
41 Sheldrick GM. SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallogr Sect A 2015; A71: 3-8.
| Crossref | Google Scholar | PubMed |
42 Sheldrick GM. Crystal structure refinement with SHELXL. Acta Crystallogr Sect C 2015; C71: 3-8.
| Crossref | Google Scholar | PubMed |
