3-甲氧基苯乙酮的合成Reaction_08_23_2013_095350

1. 2 StepsOverviewSteps/Stages Notes1.1R:DBU, S:CH2Cl2, 24 h, rt2.1C:I2, 2 h, 85°C1) modified literature procedure, 2) greenchemistry, sealed vial used under air, nosolvent, Reactants: 2, Reagents: 1, Catalysts:1, Solvents: 1, Steps: 2, Stages: 2, Moststages in any one step: 1ReferencesIodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reactionconditionsBy Jereb, Marjan and Vrazic, DejanFrom Organic & Biomolecular Chemistry,11(12), 1978-1999; 2013CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.2. Single Step84%88%OverviewSteps/Stages Notes1.1C:I2, 2 h, 85°C green chemistry, sealed vial used under air, nosolvent, Reactants: 1, Catalysts: 1, Steps: 1,Stages: 1, Most stages in any one step: 1ReferencesIodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reactionconditionsBy Jereb, Marjan and Vrazic, DejanFrom Organic & Biomolecular Chemistry,11(12), 1978-1999; 2013CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.3. Single Step100%OverviewSteps/Stages Notes1.1C:25360-32-1, C:PPh3, S:Mesitylene, 24 h, 165°C glove box used, use of Shvo's complexresulted in similar yield, Reactants: 1,Catalysts: 2, Solvents: 1, Steps: 1, Stages: 1,Most stages in any one step: 1ReferencesAcceptorless and base-free dehydrogenationof alcohols and amines using ruthenium-hydride complexesBy Muthaiah, Senthilkumar and Hong, SoonHyeokFrom Advanced Synthesis & Catalysis,354(16), 3045-3053, S3045/1-S3045/12;2012CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.4. Single Step85%OverviewSteps/Stages Notes1.1R:Me2CO, C:1417441-46-3, C:t-BuOK, 10 min, 56°C acetone used also as solvent, Reactants: 1,Reagents: 1, Catalysts: 2, Steps: 1, Stages: 1,Most stages in any one step: 1ReferencesA Versatile Ruthenium(II)-NNC ComplexCatalyst for Transfer Hydrogenation ofKetones and Oppenauer-Type Oxidation ofAlcoholsBy Du, Wangming et alFrom Chemistry - A European Journal,18(37), 11550-11554, S11550/1-S11550/11;2012CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.5. Single Step95%OverviewSteps/Stages Notes1.1C:1418299-84-9, C:139362-04-2, S:PhMe, 24 h, 120°C in-situ generated catalyst, Reactants: 1,Catalysts: 2, Solvents: 1, Steps: 1, Stages: 1,Most stages in any one step: 1ReferencesCobalt-Catalyzed Acceptorless AlcoholDehydrogenation: Synthesis of Imines fromAlcohols and AminesBy Zhang, Guoqi and Hanson, Susan K.From Organic Letters, 15(3), 650-653; 2013 CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.6. Single Step95%OverviewSteps/Stages Notes1.1R:K2CO3, S:Me2CO, 60 min, 50-55°C Reactants: 2, Reagents: 1, Solvents: 1, Steps:1, Stages: 1, Most stages in any one step: 1ReferencesA low-waste process to Rivastigmine bywaste isomer racemizationBy Reddy, Ganta Madhusudhan et alFrom Chemistry & Biology Interface, 1(2),192-197; 2011CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.7. Single Step84%OverviewSteps/Stages Notes1.1R:SnCl2, R:TiCl3, R:HCl, S:H2O, S:THF, 4 h, rt Reactants: 1, Reagents: 3, Solvents: 2, Steps:1, Stages: 1, Most stages in any one step: 1ReferencesSnCl2/TiCl3-mediated deoximation of oximesin an aqueous solventBy Lin, Mei-Huey et alFrom Molecules, 17, 2464-2473; 2012 CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.8. Single Step17%OverviewSteps/Stages Notes1.1R:NaOBu-t, C:(Ph2P)2-ferrocene, C:Pd2(dba)3, S:THF Reactants: 2, Reagents: 1, Catalysts: 2,Solvents: 1, Steps: 1, Stages: 1, Most stagesin any one step: 1ReferencesExperimental Procedure(3-Methoxy)acetophenone (263): To a solution of 3-bromoanisole (0.06 mL, 0.5 mmol) in THF (5 mL)Na-t-BuO (106 mg, 1.1 mmol), DPPF (25 mg, 0.045 mmol), and Pd2(dba)3 (17 mg, 0.02 mmol) wereadded sequentially and the resulting mixture heated at 70 degC for 28 hr with stirring under N2. Thereaction mixture was allowed to cool, then diluted with ether (25 mL), and washed with water (25 mL).The organic layer was dried over MgSO4, filtered, and evaporated in vacuo to give a crude oil. Flashchromatography eluting with 3 % EtOAc-petrol afforded ketone 263 (13 mg, 17 %) as a colourless oil. CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.9. Single StepOverviewSteps/Stages Notes1.1C:174677-83-9, C:12112-67-3, S:CH2Cl2, > 1 min, rt1.2C:Ph3PN=PPh3 •Cl, S:H2O, 1 h, rt1.3R:KOH, 0.5 h, rt1.4 6.5 h, 28°Cstereoselective, 2-propanol/product also usedas solvent (stage 3), in-situ generated catalyst(stage 1), phase transfer catalyst used (stage2), 59% conversion, 91% ee of chiral alcoholobtained, oxidative kinetic resolution ofracemic secondary alcohol, green chem.-solvent, Reactants: 2, Reagents: 1, Catalysts:3, Solvents: 2, Steps: 1, Stages: 4, Moststages in any one step: 4ReferencesOxidative kinetic resolution of racemicsecondary alcohols in water with chiralPNNP/Ir catalystBy Zhang, Juanni et alFrom Green Chemistry, 14(5), 1289-1292;2012CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.10. Single Step87%OverviewSteps/Stages Notes1.1S:MeCN, 10 h, rt → 150°C1.2R:HCl, S:H2O, > 1 min, 150°C → 40°Csolvothermal in stage 1, Teflon liner fixedautoclave used in stage 1, thermal in stage 1,mechanism studied, Reactants: 2, Reagents:1, Solvents: 2, Steps: 1, Stages: 2, Moststages in any one step: 2ReferencesSynthesis of aryl ketones via decarboxylationof aromatic acids under solvothermalconditionBy Rai, K. M. Lokanatha et alFrom Asian Journal of Chemistry, 24(3),1395-1396; 2012CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.11. 2 Steps[Step 2.1]OverviewSteps/Stages Notes1.1R:HBF4, R:NaNO22.1S:MeOH, 18 h, 60°CReactants: 2, Reagents: 2, Solvents: 1, Steps:2, Stages: 2, Most stages in any one step: 1ReferencesAryl ethers from arenediazoniumtetrafluoroborate salts: from neat reactions tosolvent-mediated effectsBy Shriver, James A. et alFrom Journal of the Iowa Academy ofScience, 116(1-4), 27-35; 2010CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.12. Single Step30%OverviewSteps/Stages Notes1.1S:MeOH, 18 h, 60°C Reactants: 2, Solvents: 1, Steps: 1, Stages: 1,Most stages in any one step: 1ReferencesAryl ethers from arenediazoniumtetrafluoroborate salts: from neat reactions tosolvent-mediated effectsBy Shriver, James A. et alFrom Journal of the Iowa Academy ofScience, 116(1-4), 27-35; 2010CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.13. Single Step93%OverviewSteps/Stages Notes1.1R:H2O, C:12651-22-8, S:292-64-8,2.5 h, 100°C catalyst prepared and used, green chem.-reusable catalyst, Reactants: 1, Reagents: 1,Catalysts: 1, Solvents: 1, Steps: 1, Stages: 1,Most stages in any one step: 1ReferencesHeterogeneously Catalyzed EfficientHydration of Alkynes to Ketones by Tin-Tungsten Mixed OxidesBy Jin, Xiongjie et alFrom Chemistry - A European Journal, 17(4),1261-1267; 2011CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.14. Single Step86%OverviewSteps/Stages Notes1.1R:KOH, S:MeOH, 2 h, rt green chemistry-process simplification, greenchemistry-waste reduction, electrochemical(1.9 V), three-electrode cell assembly with Ptplate as working and counter electrode andsaturated calomel electrode as referenceelectrode used, mechanism studied,preparative scale, controlled potentialelectrolysis, Reactants: 2, Reagents: 1,Solvents: 1, Steps: 1, Stages: 1, Most stagesin any one step: 1ReferencesElectro-organic nuclear oxidation:methoxylation of aromatic compounds atplatinum electrodeBy Kumar, SanjeevFrom E-Journal of Chemistry, 8(2), 846-850;2011CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.15. Single Step88%OverviewSteps/Stages Notes1.1R:KOH, C:111216-21-8, C:Pd(OAc)2, S:(CH2OH)2, 10 h, 145°C;145°C → rt1.2R:HCl, S:H2O, 1 h, rtregioselective, Heck reaction, mechanismstudied, carousel reaction tube used,Reactants: 2, Reagents: 2, Catalysts: 2,Solvents: 2, Steps: 1, Stages: 2, Most stagesin any one step: 2ReferencesHydrogen-Bonding-Promoted OxidativeAddition and Regioselective Arylation ofOlefins with Aryl ChloridesBy Ruan, Jiwu et alFrom Journal of the American ChemicalSociety, 132(46), 16689-16699; 2010Experimental ProcedureGeneral/Typical Procedure: General Procedure for the Heck Arylation of Olefins: An oven-driedcarousel reaction tube containing a stirrer bar was charged with aryl chloride 1 (1.0 mmol), Pd(OAc)2(0.01 mmol), 4-MeOdppp (0.015 mmol), and KOH (1.5 mmol). After degassing three times withnitrogen, ethylene glycol (4 mL) and n-butyl vinyl ether 2a (3.0 mmol) were injected sequentially. Thereaction mixture was vigorously stirred at 145 °C for 10 h. After cooling down to room temperature, 2mL aqueous HCl (3 M) and 10 mL Et2O were added; the mixture was stirred for 1 h. After separation ofthe Et2O phase, the aqueous layer was extracted with Et2O (3 x 10 mL) and the combined organiclayers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo (When aqueoushydrolysis was not necessary, the product was directly extracted from EG with Et2O). The crudeproduct was purified by flash chromatography on silica gel using a mixture of ethyl acetate and hexane(5/95 to 50/50) as eluant. 3'-Methoxylacetophenone (3l), yield 88%. 1H NMR (400 MHz, CDCl3) δ 7.53(d, J = 8.0 Hz, 1H), 7.49 (d, J = 2.0 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.11 (dd, J = 2.0, 8.0 Hz, 1H),3.85 (s, 3H), 2.60 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 198.4, 160.2, 138.9, 130.0, 121.5, 120.0,112.8, 55.8, 27.1; MS (CI, m/z, %) 151 (100) [M+H]+; Anal. calcd for C9H10O2: C, 71.98; H, 6.71.Found: C, 71.87; H, 6.71.CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.16. Single Step96% (6:4:90 )96% (6:4:90 )96% (6:4:90 )OverviewSteps/Stages Notes1.1R:AlCl3, S:CCl4, 2 d, reflux1.2 1.5 h, 80°Cin-situ generated catalyst, Friedel-Craftsacylation, green chemistry, no solvent, solidsupported catalyst used, regioselective (stage2), Reactants: 2, Reagents: 1, Solvents: 1,Steps: 1, Stages: 2, Most stages in any onestep: 2ReferencesFriedel-Crafts acylation of arenes withcarboxylic acids using silica gel supportedAlCl3By Boroujeni, Kaveh ParvanakFrom Turkish Journal of Chemistry, 34(4),621-630; 2010CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.17. Single Step95%OverviewSteps/Stages Notes1.1R:K2CO3, S:Me2CO, 1 h, 45°C; 1 h, 45°C; 45°C → 25°C1.2R:H2Oscalable, reaction with dimethylcarbonate orMeI/K2CO3 not completed, Reactants: 2,Reagents: 2, Solvents: 1, Steps: 1, Stages: 2,Most stages in any one step: 2ReferencesAn improved process for the production ofrivastigmine tartrate, a cholinesterase inhibitorBy Reddy, Vajrala Venkata et alFrom Letters in Organic Chemistry, 7(2), 149-154; 2010CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.18. 3 Steps[Step 2.2]OverviewSteps/Stages Notes1.1R:NaH, S:THF, 30 min, 0°C1.2R:SOCl2, 0°C → rt1.3R:C5H5N, rt; 12 h, reflux2.1R:BuLi, S:THF, S:Me(CH2)4Me, 30 min, 0°C; 0°C → rt2.230 min, rt3.1R:Ce(NH4)2(NO3)6, S:H2O, S:MeCN, 0°C; 3 h, rt Reactants: 3, Reagents: 5, Solvents: 4, Steps: 3, Stages: 6, Most stages in any one step: 3ReferencesPara-Quinone-Containing Bis(pyrazol-1-yl)methane Ligands: Coordination Behavior Toward CoII and a C-H Activation Reaction with CeIVBy Blasberg, Florian et alFrom Inorganic Chemistry, 49(16), 7435-7445; 2010Experimental ProcedureStep 1General/Typical Procedure: Synthesis of L3Me2. In a representative procedure, n BuLi (1.52 M inhexane; 1.93 mL, 2.9 mmol) was added at 0 °C via syringe to a stirred solution of L2Me2 (1.00 g, 2.9mmol) in THF (40 mL).After 30min, the bright red reaction mixture was allowed to warm to roomtemperature, and neat MeI (0.18 mL, 0.41 g, 2.9 mmol) was added via syringe, whereupon the redcolor vanished rapidly. Stirring was continued for another 30 min. The reaction mixture was poured intoH2O (30 mL), and L3Me2 was extracted into CH2Cl2 (3 x 20 mL). The combined extracts were driedover MgSO4 and filtered, and the filtrate was evaporated to dryness. The crude product was trituratedwith hexane and recrystallized from hot hexane. Synthesis of S2. The compound was preparedfollowing the representative procedure described for L2Me: NaH (0.50 g, 20.8 mmol), THF (80 mL),3,5-dimethylpyrazole (2.00 g, 20.8 mmol), SOCl2 (0.76 mL, 1.24 g, 10.4 mmol), 3-methoxybenzaldehyde (1.27 mL, 1.42 g, 10.4 mmol), pyridine (0.84 mL, 0.82 g, 10.4 mmol). The crude productwas adsorbed on silica gel and purified via column chromatography (silica gel; hexane/EtOAc 1:1).Yield: 1.51 g (47%); colorless oil. R f = 0.55 (silica gel; hexane/EtOAc 1:1). 1H-NMR (250.1 MHz,C6D6) δ = 2.14, 2.17 (2 × s, 2 × 6 H; pz-CH3), 3.17 (s, 3 H; OCH3), 5.66 (s, 2 H; pz-H4), 6.65, 6.75 (1 ×dd, 1 × m, 3J HH = 8.2 Hz, 4J HH = 2.3 Hz, 2 × 1 H; Ar-H2,4), 6.82 (vt, 1 H; Ar-H6), 6.98 (vt, 1 H; Ar-H3), 7.83 (s, 1 H; CH). 13C-NMR (62.9 MHz, C6D6) δ = 11.9, 13.8 (pz-CH3), 54.7 (OCH3), 74.5 (Cpz2),107.0 (pz-C4), 113.4 (Ar-C6), 114.0, 119.7 (Ar-C2,4), 129.7 (Ar-C3), 139.3 (Ar-C1), 141.1, 148.2 (pz-C3,5), 160.5 (Ar-C5). ESI-MS: m/z (%) = 215 [M - pzMe2]+ (100), 311 [M + H]+ (34). Anal. Calcd forC18H22N4O [310.39]: C 69.65, H 7.14, N 18.05. Found: C 69.61, H 7.30, N 17.77.Step 2General/Typical Procedure: Synthesis of L3Me2. In a representative procedure, n BuLi (1.52 M inhexane; 1.93 mL, 2.9 mmol) was added at 0 °C via syringe to a stirred solution of L2Me2 (1.00 g, 2.9mmol) in THF (40 mL).After 30min, the bright red reaction mixture was allowed to warm to roomtemperature, and neat MeI (0.18 mL, 0.41 g, 2.9 mmol) was added via syringe, whereupon the redcolor vanished rapidly. Stirring was continued for another 30 min. The reaction mixture was poured intoH2O (30 mL), and L3Me2 was extracted into CH2Cl2 (3 x 20 mL). The combined extracts were driedover MgSO4 and filtered, and the filtrate was evaporated to dryness. The crude product was trituratedwith hexane and recrystallized from hot hexane. Synthesis of M2. The compound was preparedfollowing the representative procedure described for L3Me2: S2 (1.46 g, 4.7 mmol), n BuLi (1.52 M inhexane; 3.1 mL, 4.7 mmol), MeI (0.29 mL, 0.66 g, 4.7 mmol). The crude product was purified bycolumn chromatography (silica gel; hexane/EtOAc 3:1). Yield: 0.79 g (52%); colorless oil. R f = 0.46(silica gel; hexane/EtOAc 3:1). 1H-NMR (400.1 MHz, C6D6) δ = 1.65, 2.19 (2 × s, 2 × 6 H; pz-CH3),2.59 (s, 3 H; CH3),3.27 (s, 3 H; OCH3), 5.73 (s, 2 H; pz-H4), 6.64, 6.77 (1 × dd, 1 × m, 3J HH = 8.2 Hz,4J HH = 2.3 Hz, 2 × 1 H; Ar-H2,4), 6.89 (vt, 1 H; Ar-H6), 7.02 (vt, 1 H; Ar- H3). 13C-NMR (100.6 MHz,C6D6) δ = 11.9, 13.8 (pz-CH3), 32.4 (CH3), 54.7 (OCH3), 83.6 (Cpz2), 108.7 (pz-C4), 113.1 (Ar-C2 or4), 115.2 (Ar-C6), 120.5 (Ar-C2 or 4), 128.7 (Ar- C3), 141.3, 144.4, 146.0 (Ar-C1, pz-C3,5), 160.0 (Ar-C5). ESI-MS: m/z (%) = 229 [M - pzMe2]+ (100), 325 [M + H]+ (35). Anal. Calcd for C19H24N4O[324.42]: C 70.34, H 7.46, N 17.27. Found: C 70.68, H 7.71, N 16.41.Step 3General/Typical Procedure: Synthesis of L4Ph. In a representative procedure, [Ce(NH4)2(NO3)6] (2.63g, 4.8 mmol) in H2O(20 mL) was added at 0 °C to a stirred solution of L3Ph (0.72 g, 1.6 mmol) inMeCN (20 mL). The mixture was allowed to warm to room temperature, and stirring was continued for3 h. The product was extracted into CH2Cl2 (3 x 50 mL). The combined extracts were dried overMgSO4 and filtered, and the filtrate was evaporated to dryness under reduced pressure.CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.19. 2 StepsOverviewSteps/Stages Notes1.1R:BuLi, S:THF, S:Me(CH2)4Me, 30 min, 0°C; 0°C → rt1.230 min, rt2.1R:Ce(NH4)2(NO3)6, S:H2O, S:MeCN, 0°C; 3 h, rtReactants: 2, Reagents: 2, Solvents: 4, Steps:2, Stages: 3, Most stages in any one step: 2ReferencesPara-Quinone-Containing Bis(pyrazol-1-yl)methane Ligands: Coordination BehaviorToward CoII and a C-H Activation Reactionwith CeIVBy Blasberg, Florian et alFrom Inorganic Chemistry, 49(16), 7435-7445; 2010Experimental ProcedureStep 1General/Typical Procedure: Synthesis of L3Me2. In a representative procedure, n BuLi (1.52 M inhexane; 1.93 mL, 2.9 mmol) was added at 0 °C via syringe to a stirred solution of L2Me2 (1.00 g, 2.9mmol) in THF (40 mL).After 30min, the bright red reaction mixture was allowed to warm to roomtemperature, and neat MeI (0.18 mL, 0.41 g, 2.9 mmol) was added via syringe, whereupon the redcolor vanished rapidly. Stirring was continued for another 30 min. The reaction mixture was poured intoH2O (30 mL), and L3Me2 was extracted into CH2Cl2 (3 x 20 mL). The combined extracts were driedover MgSO4 and filtered, and the filtrate was evaporated to dryness. The crude product was trituratedwith hexane and recrystallized from hot hexane. Synthesis of M2. The compound was preparedfollowing the representative procedure described for L3Me2: S2 (1.46 g, 4.7 mmol), n BuLi (1.52 M inhexane; 3.1 mL, 4.7 mmol), MeI (0.29 mL, 0.66 g, 4.7 mmol). The crude product was purified bycolumn chromatography (silica gel; hexane/EtOAc 3:1). Yield: 0.79 g (52%); colorless oil. R f = 0.46(silica gel; hexane/EtOAc 3:1). 1H-NMR (400.1 MHz, C6D6) δ = 1.65, 2.19 (2 × s, 2 × 6 H; pz-CH3),2.59 (s, 3 H; CH3),3.27 (s, 3 H; OCH3), 5.73 (s, 2 H; pz-H4), 6.64, 6.77 (1 × dd, 1 × m, 3J HH = 8.2 Hz,4J HH = 2.3 Hz, 2 × 1 H; Ar-H2,4), 6.89 (vt, 1 H; Ar-H6), 7.02 (vt, 1 H; Ar- H3). 13C-NMR (100.6 MHz,C6D6) δ = 11.9, 13.8 (pz-CH3), 32.4 (CH3), 54.7 (OCH3), 83.6 (Cpz2), 108.7 (pz-C4), 113.1 (Ar-C2 or4), 115.2 (Ar-C6), 120.5 (Ar-C2 or 4), 128.7 (Ar- C3), 141.3, 144.4, 146.0 (Ar-C1, pz-C3,5), 160.0 (Ar-C5). ESI-MS: m/z (%) = 229 [M - pzMe2]+ (100), 325 [M + H]+ (35). Anal. Calcd for C19H24N4O[324.42]: C 70.34, H 7.46, N 17.27. Found: C 70.68, H 7.71, N 16.41.Step 2General/Typical Procedure: Synthesis of L4Ph. In a representative procedure, [Ce(NH4)2(NO3)6] (2.63g, 4.8 mmol) in H2O(20 mL) was added at 0 °C to a stirred solution of L3Ph (0.72 g, 1.6 mmol) inMeCN (20 mL). The mixture was allowed to warm to room temperature, and stirring was continued for3 h. The product was extracted into CH2Cl2 (3 x 50 mL). The combined extracts were dried overMgSO4 and filtered, and the filtrate was evaporated to dryness under reduced pressure.CASREACT ®: Copyright © 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.20. Single Step。