activation of CH bonds of phenols catalyzed by copper amine complexes Mebrouka Dekhici ab Didier Villemin a Nawel Cheikh bc Nathalie Bar a a Laboratoire de Chimie Moléculaire et ID: 1011608
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1. Aerobic and biomimetic activation of C-H bonds of phenols catalyzed by copper-amine complexesMebrouka Dekhici,a,b Didier Villemina*, Nawel Cheikhb,c, Nathalie Baraa Laboratoire de Chimie Moléculaire et Thioorganique, UMR CNRS 6507, INC3M, FR 3038, ENSICAEN et Université de Caen Normandie, 14050 Caen, Franceb Université de Bechar, Faculté des Sciences et Technologies, BP 417, 08000 Bechar, AlgeriacLaboratoire de Catalyse Et Synthèse en Chimie Organique, Faculté des Sciences, Université de Tlemcen, BP 119, 13000, Tlemcen, AlgeriaE-mail: didier.villemin@ensicaen.fr1sciforum-050847 The 25th International Electronic Conference on Synthetic Organic Chemistry
2. IntroductionSome products formed by oxidative coupling of phenolsBiomimetic phenol couplings studied by D.H.R. Barton and A.R. Battersby since 1950.Oxidases (Laccase or Tyrosinase) Copper-amine model catalysts CuCl(OH) TMEDA W. I. Taylor, A. R. Battersby, D. H. R. Barton, T. Cohen, Festschrift Arthur Stoll., Birkhauser, Basel 1957, 117–143.
3. CuClCuCl2[CuCl(OH)TMEDA]2 Cu(I)/PEIIron complexe: Copper complexesPreparation of the complexesCuCl(phen)CuCl(neocup)CuCl(bipy) CuCl2- Bis(1,3-propanediamine)
4. Copper complexesPreparation of the complexesa) CuCl2
5. [CuCl(OH)TMEDA]2 Cu(I)/PEICopper complexesb) CuClPreparation of the complexes
6. Oxidative coupling of the phenolComplexeRdt (%)CuCl(OH).TMEDA 71Cu(I)/PEI 31CuCl(phen) 17CuCl(neocup) 39CuCl(bipy) 9CuCl2- Bis(1,3-propanediamine) 41[Fe(DMF)3Cl][FeCl4] 63[CuCl(OH)TMEDA]2 Cu(I)/PEIOxidation conditions:Phenol/Cu (100/8) Phenol/Fe (100/8) Room temperature(20°C), EtOH, 120h.para-cresolS. E. Allen, R. R. Walvoord, R. Padilla-Salinas, M. C. Kozlowski, Aerobic Copper-Catalyzed Organic Reactions, Chem. Rev. 2013, 113, 6234–6458 ; doi :10.1021/cr300527g
7. Oxidative coupling of the phenolOxidation of phenols in the presence of [CuCl(OH)(TMEDA)]2 ortho-ortho coupling Substrate: the para position is blocked or difficult to accessCouplage ortho-ortho coupling Oxidation conditions: Phenol/Cu (100/8) 21°C EtOH 96h.
8. Oxidative coupling of the phenolOxidation of the phenols in presence of [CuCl(OH)(TMEDA)]2 Para-para coupling QuinoneBisphenolDiphenoquinone
9. Oxidative para-para coupling of phenolspara-para couplingOxidation conditions Phenol / Cu (100 / 8) Room temperature 21°CEtOH 96 h.Oxidation of phenol in the presence of CuCl(OH)(TMEDA)
10. Oxidative para-para coupling of phenolsOxidation of phenols in the présence of Cu(I)/PEI Oxidation conditions: Phenol / Cu (100 / 3.75) (1.5mL)Room temperatureEtOH120 h.
11. Oxidation of phenolsOxidation of phenols in the presence of NHPI: formation of quinoneNHPI = N-hydroxyphthalimide Oxidation conditions: Phenol/Cu/NHPI (100/8/10) 96 h.SolventTemperature (°C)Yield (%)EtOH 2116EtOH 7027CH3CN 2132CH3CN 7092Best conditions for formation of p-quinone70°C in acetonitrile
12. Oxidation of phenolsOxidation of phenols in the presence of NHPICatalystYield (%)CuCl(OH)TMEDA 92Cu(I)/PEI 0CuCl2(neocup) 0[Fe(DMF)3Cl][FeCl4] 0Oxidation conditions : Phenol/Cu/NHPI (100/8/10) Phenol/Fe/NHPI (100/8/10) 70°C CH3CN 96 h
13. Synthesis of purpurogallin from pyrogallol Purpurogallin: naturel red dyetropoloneSynthesis of purpurogallin by oxidation : Stoichiometric oxidation (KIO3) Oxidases : laccase, tyrosinase, peroxidase Mechanism according to Haworth
14. Synthesis of purpurogallin from pyrogallol Synthesis of Purpurogallin by aerobic oxidation like LaccaseConditions :[a] Phenol/Cu (100/8), 20°C, EtOH, 96h[b] Phenol/Cu(I)/(100/3.75) (1.5 mL), 20°C, EtOH, 96h[c] Phenol/Cu/NHPI (100/8/10), 70°C, CH3CN, 96 h CatalystSolventT (ºC)Yield(%)CuCl(OH)TMEDAa EtOH2043Cu(I)/PEIb EtOH200CuCl(OH)TMEDA / NHPIc CH3CN700S. Dib ; D. Villemin; A. Hamhami; B. Mostefa-Kara; N. Bar; M. Dekhici ; N. Cheikh, On the green catalytic synthesis of Purpurogallin, Rev. Roum. Chim.,2020, 65(12), 1153-1157, doi: 10.33224/rrch.2020.65.12.1.
15. Oxydation of 2-naphthols Oxidation of 2-naphthols and analoguesOxidative conditions:[a] naphthol/catalyst (100/8), 96h. [b] naphthol/catalyst ( /NHPI (100/8/10), 96 h.[c] naphthol/catalyst ( (100/3.75) (1.5 mL), 96h. CatalystSolventT (°C)Yield (%)CuCl(OH)TMEDAa EtOH2186CuCl(OH)TMEDA / NHPIb CH3CN7043Cu(I)/PEIc EtOH2177CuCl2(phen)a EtOH2129CuCl2(neocup) a EtOH2131CuCl2(bipy) a EtOH21tracesCuCl2-Bis(1,3-propanediamine) a EtOH2171[Fe(DMF)3Cl][FeCl4] a EtOH2155
16. Oxydation des 2-naphtols et analoguesOxidation of naphthols Conditions : [a] naphthol/Cu (100/8), 21°C, EtOH, [b]naphthol/Cu/NHPI (100/8/10), 70°C, CH3CN,
17. Oxidation of methylenebinaphthols andt benzylidenebinaphtholsOxidation of methylenebinaphthols and benzylidenebinaphtholsOxidative conditions:Phenol/Cu (100/8) AirRoom temperature(21°C)SolventTime (48 h)Creation of C-O bondDesaromatisationGreen conditionsM. Dekhici ; S. Plihon, N. Bar ; D.Villemin ; H. Elsiblani ; N. Cheikh, Aerobic Copper Catalytic Oxidation of Methylene and Arylidenebisnaphthols: A Green and Efficient Synthesis of Spironaphthalenones , ChemistrySelect , 2019, 4, 705 - 708 ; doi: 10.1002/slct.201803153