Furfural Obtained from Pentoses A Valuable Synthon for Fine Chemistry

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1 Université de eims Champagne-Ardenne Furfural btained from Pentoses A Valuable Synthon for Fine Chemistry orbert offmann CS, Université de eims ICM Équipe de Photochimie eims, France

2 Production of Furfural Pentose containing biomass, hemicelluloses Cyclodehydration Furfural Worldwide production: Production in China: > tpa tpa J.-. wang et al. Biofuels, Bioprod. Bioref. 2008, 2, 438. B. Kamm, P.. Gruber, M. Kamm (Eds.), Biorefineries Industrial Processes and Products. Wiley-VC, Weinheim, J.. Chheda, G. W. uber, J. A. Dumesic, Angew. Chem. Int. Ed. 2007, 46, 7164.

3 eduction of Furfural Me Me Br n J.. Chheda, G. W. uber, J. A. Dumesic, Angew. Chem. Int. Ed. 2007, 46, 7164.

4 xydation of Furfural Furoic Acid ' C 3 2 sens ' Pyranone V(acac) 2 t-bu 86% 2 /cat 2 2 C 2 51% or % ydroxyfuranone Furanone

5 Pyranones as Versatile Synthons monosaccharides, KD liposaccharides, glycosides, antibiotics, (e.g. vineomycin, aclacinomycin, nogalamycin) annulated pyranosides e.g. antibiotics actinobolin, forskolin aminosugars, thiosugars, sugaryl aminoacids, azasugars (e.g. indolizidines) 2 1 penicilic acid derivatives X 1 3 frontalin, multistriatin disaccharides, antibiotics (e.g. tirantamycin) eactions with Diene Conversion to levoglucosenones eaction with Michael and/or suaryl donors antimicrobials antifungals anticoccidials antitumors cardiac stgeroids pesticides herbicides ther reactions Conversion to other synthetic building blocks (Wittig coupling) (cyclopropanation) chrysanthemo carboxylic acids Conversion to pyrones benzodiazepinones, thiazepinones, etc. ther natural products e.g. pseudomonic acid, styryl lactones, aspertin, spirolactones pheromones and antibiotics Conversion to polyhudroxylated chains e.g. monocrotalic acid macrolide and ionophoric antibiotics 3 1 Prelog-Djerassilactone cyclopentanones 1 2 butenolides E. A. Couladouros, A. T. Strongilos, Angew. Chem. Int. Ed. 2002, 41, 3677

6 ydroxyfuranone as a Versatile Synthon PhS C 2 Me 2 C 2 C 2 C 2 Me C 2 F Me 2 2 C C 2 Ac Insecticides, fungicides, quick-drying varnishes X C C 2 C C 2

7 Menthyloxyfuranone as a Versatile Chiral Synthon alkene Michael acceptor ester acid 5 allyllic group aldehyde chiral acetale

8 Menthyloxyfuranone as a Versatile Chiral Synthon X ( ) n Y Ar Me Me MeC Me C C ' Br Br C C Me Me Me C 2 3 Cl - ( ) n Ph 2 P PPh 2 1 n 1 2 Bu X 2 1 C 2 1 C X X C

9 Synthesis of (5)- and (5S)-((-)-Menthyloxy)-2[5]-furanone C 2, sens, Me 91% (-)-Menthol 3 3 1' 1' 5 5 mp = 79 C mp = 41 C (5)-(l)-Menthyloxyfuran-2[5]-on (5S)-(l)-Menthyloxyfuran-2[5]-on S. Marinkovic, C. Brulé,. offmann, E. Prost, J.-M. uzillard, V. Bulach, J. rg. Chem. 2004, 69, 1646

10 adical-tandem-eaction with (5)- and (5S)-((-)-Menthyloxy)-2[5]-furanone 5 sens. Aceton 91% de 5 21 : % 5 S sens. Aceton 5 53% de S 3.3 : 1 44% 5 S S. Marinkovic, C. Brulé,. offmann, E. Prost, J.-M. uzillard, V. Bulach, J. rg. Chem. 2004, 69, %

11 Conformation Analysis of (5)- and (5S)-((-)-Menthyloxy)-2[5]-furanone S

12 Double Induction with (5)- and (5S)-((-)-Menthyloxy)-2[5]-furanone 5 5 P(syn) / P(anti) : 21 / 1 P'(syn) / P'(anti) : 3 / 1 S Matched Mismatched ln (P(syn) / P(anti)) = -(ΔΔG a ΔΔG menth ) / T ln (P'(syn) / P'(anti)) = -(ΔΔG a - ΔΔG menth ) / T ΔΔG a = kcal.mol -1 ΔΔG menth = kcal.mol -1

13 adical Addition of Tertiary Amines to Electron Deficient Alkenes (λ=350nm) sens. 94% Φ = 4 1 : 1.2 sens. : Me Me Me 2 Me 2 S. Bertrand,. offmann, J.-P. Pete, Eur. J. rg. Chem. 2000, A. G. Griesbeck,. offmann, K.-D. Warzecha, Acc. Chem. es. 2007, 40, 128

14 Comparing ew and Conventional Sensitizers ew Sensitizers igh yields (>90%) Fast reactions (15g after 5min of irradiation) Catalytic amounts ecovery up to 80% after the reaction Conventional Sensitizers (benzophenone, acetophenone) Modest yields (~40%) Slow reactions At least stoechiometric amounts Degradation of the sensitizer Formation of many side products. offmann, J. Photochem. Photobiol. C: Photochem. ev. 2008, 9, 43 See also:. offmann,. Görner, Chem. Phys. Lett. 2004, 383, 451

15 Mechanism of the adical Addition of tertiary Amines to Electron Deficient Alkenes I II Me Me Me Me S. Bertrand,. offmann, J.-P. Pete, Eur. J. rg. Chem. 2000, See also: S. Bertrand,. offmann, S. umbel, J.-P. Pete, J. rg. Chem. 2000, 65, offmann, Chem. ev. 2008, 108, 1052.

16 Asymmetric Synthesis of ecines and Indolizidines /sens. 94% /sens. 46% Menth Menth Menth ab 4 80% ab 4 83% ab 4 79% =t-bu TFA/C 2 Cl 2 79% =Me; /DCA /DCA 81% LiCl 4 /MeC LiCl 4 /MeC 83% LiAl 4 86% LiAl 4 78% LiAl 4 88% (-)-Isoretronecanol 23% ()-Laburnin 27% 27% S. Bertrand,. offmann, J.-P. Pete, Eur. J. rg. Chem. 2000, 2227.

17 Semiconductor Catalyzed adical Addition of Tertiary Amines with Electron Deficient Alkenes SC Menth Menth 1 : 1.2 Semiconductor a c(furanone) [mol/l] c(amine) [mol/l] Time of Irradiation [h] Conversion [%] Yield b [%] Ti ZnS Ti solvent ZnS 10-2 solvent Ti solvent Ti solvent a) 2 mol-% with respect to the furanone. b) Based on conversion of the furanone. S. Marinkovic,. offmann, Chem. Commun. 2001, 1576 S. Marinkovic,. offmann, Intern. J. Photoenergy 2003, 5, 175

18 Semiconductor Catalyzed adical Addition of Tertiary Amines with Electron Deficient Alkenes ' Ti 2 ' ' 1 : 1.2 Time of Irradiation [h] Conversion [%] Yield a [%] Et b Menth a) Based on conversion of the α,β-unsaturated lactone. b) The starting concentration was 10-2 mol/l. S. Marinkovic,. offmann, Chem. Commun. 2001, 1576 S. Marinkovic,. offmann, Intern. J. Photoenergy 2003, 5, 175

19 Mechanism of the Semiconductor Catalyzed adical Addition of Tertiary Amines with Alkenes Conduction band e -, e - ecombination Valence band h -e -, - Semiconductor particle S. Marinkovic,. offmann, Chem. Commun. 2001, 1576 S. Marinkovic,. offmann, Intern. J. Photoenergy 2003, 5, 175

20 adical Tandem eaction of Aromatic Tertiary Amines with Electron Deficient Alkenes λ=350nm Menth Menth sensitizer: Me 2 Me 2 38% 1.7% Menth 18% 7% Menth Menth S. Bertrand,. offmann, S. umbel, J.-P. Pete, J. rg. Chem. 2000, 65, offmann, S. Bertrand, S. Marinkovic, J. Pesch, Pure Appl. Chem. 2006, 78, 2227

21 Me 2 sens Me 2 3 sens * Me 2 Me 2 Menth Menth Menth Menth Menth eplace by an oxydant Menth Menth

22 adical Tandem eaction of Aromatic Tertiary Amines with Electron Deficient Alkenes λ=350nm sensitizer acetone Menth Menth 74% 3% λ=350nm sensitizer acetone Menth 56% 90% de λ=350nm sensitizer acetone Menth Menth 39% 32% λ=350nm sensitizer acetone Menth Menth 48% 26% S. Bertrand,. offmann, S. umbel, J.-P. Pete, J. rg. Chem. 2000, 65, 8690

23 ' ' " Ester γ-aminobutytique Pyrrolidines Pipéridines Tetrahydroquinolines Pyrrolizidines Indolizidines n n Azasteroïdes Benzoindolizidines Benzoquinolizidines Perhydroazazulènes

24 Conclusions Furfural obtained from pentose containing biomass is a versatile synthon for the production of a large variety of fine chemicals Key intermediates are obtained by reduction and oxidation of furfural. ydroxyfuranones obtained by photochemical oxidation of furfural can easily be transformed into numerous biologically active target compounds such as nitrogen containing heterocycles. Transformations of products such as furfural from renewable resources in combination with environmentally friendly processes such as photochemical reactions provide perspectives for a sustainable chemical industry.

25 Thanks Dr. Emmanuel iguet Dr. Samuel Bertrand Dr. Céline Verrat Dr. Siniša Marinković Dr. Jens Pesch Dr. Abdoulaye Gassama Ali Youssef abih Jahjah ussein Mathieu Queste Dr. Frédéric Dumur Dr. Frédéric Canonne Dr. Cédric Brulé Dominique arakat Financial Support -CS -Ministère de l enseignement supérieure et de la recherche -égion Champagne-Ardenne -DFG/CS -ADEME/AGICE -EGIDE -Syngenta Crop Protection AG -Pôle de compétitivité, Industries & Agro-esources, IA Prof. Axel G. Griesbeck (Universität zu Köln) Prof. Manabu Abe (University of iroshima) Prof. Yoshihisa Inoue Dr. Tadashi Mori (University of saka) Prof. Louis Giraudet Dr. livier Simonetti (Laboratoire des ME, Université de eims) Dr. Jacques Lalevee Prof. Xavier Allonas (Université aute Alsace, Mulhouse) Prof. Stephan Landgraf (Technische Unversität Graz) Dr. elmut Görner (MPI für Bioanorganische Chemie, Mülheim/uhr) Dr. Cédric Ernenwein (Agro-Industrie echerches et Développements) Dr. Patrice Sellès (Syngenta Crop Protection AG) Dr. Michael elgemöller (Dublin City University/James Cook University) Dr. Philippe Gros (UM 7565, Université enri Poincaré, ancy) Dr. Jean-Marc uzillard, Elise Prost (UM 6013, Université de eims) Dr. Véronique Bulach (Institut Le Bel, Université Louis Pasteur, Strasbourg)

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