| 91% |
With lithium hydroxide In neat (no solvent) at 140℃; for 24h; Inert atmosphere; |
|
| 89% |
With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,2,4-Trimethylbenzene at 200℃; for 36h; Inert atmosphere; |
|
| 89% |
With NiCuFeO(x) In 5,5-dimethyl-1,3-cyclohexadiene for 24h; Inert atmosphere; Sealed tube; Reflux; |
|
| 87% |
With polystyrene supported triphenylphosphine ruthenium complex In toluene at 120℃; for 18h; Sealed tube; Flow reactor; |
|
| 86% |
With trifuran-2-yl-phosphane; palladacycle; lithium hydroxide In neat (no solvent) at 100℃; for 24h; Molecular sieve; Inert atmosphere; |
2.2. General procedure for N-alkylation of amines using benzyl alcohol
General procedure: An oven dried Schlenk tube was charged with amine (3.0 mmol), alcohol (3.6 mmol), LiOH (1.5 mmol), palladacycle (6.0*10-3 mmol, 0.20 mol %), P(2-Fur)3 (12.0*10-3 mmol, 0.40 mol %) and activated 4 Å MS (100 mg) in argon atmosphere. The reaction mixture was stirred at 100 °C for 24 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (10 mL), and washed with water followed by brine solution. The organic phase was dried over anhydrous sodium sulphate. After removal of the solvent, the crude was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the N-alkylated product. |
| 85% |
With μ-diiodo-di((η5-pentamethylcyclopentadienyl)(iodo)iridium) In water at 110℃; for 3h; Ionic liquid; Inert atmosphere; |
|
| 85% |
With 2-butyl-1,3-diphenyl-1,3,2-diazaphospholidine; 1,1'-azodicarbonyl-dipiperidine In 1,2-dichloro-ethane at 20℃; for 24h; |
|
| 84% |
In toluene for 24h; Heating; |
|
| 84% |
With 1,1'-bis(diphenylphosphino)ferrocene; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 In toluene at 20℃; Inert atmosphere; Reflux; Molecular sieve; |
|
| 83% |
With sodium hydrogencarbonate In toluene at 110℃; for 17h; |
|
| 83% |
With ionically convoluted poly(spiroborate)iridium catalyst; air at 150℃; for 24h; aq. buffer; Microwave irradiation; |
|
| 83% |
With (spiroborate)2n*[(η5-pentamethylcyclopentadienyl)(N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)iridium(III)]n In aq. buffer at 150℃; for 24h; Microwave irradiation; |
Dehydrative Alkylation of Amines with Alcohols in Water
General procedure: The appropriate amine 9 (0.5 mmol), the respective alcohol 10 (0.6mmol), PB-Cp*Ir(IPr) (3; 1 mol% Ir), and H2O (0.5 mL) were mixed in a vial tube at 23 °C under air. The vial was sealed with ascrew cap, and the reaction mixture was stirred at 100 °C for 24 h.After cooling to 23 °C, the mixture was extracted with Et2O orEtOAc (3 × 2 mL) and the combined organic layers were concentrated.The crude product was purified by column chromatographyover silica gel eluting with hexane-EtOAc (98:2 to 85:15) to affordthe corresponding N-alkylated amine 11a-n |
| 81% |
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; bis[2-(diphenylphosphino)phenyl] ether at 115℃; for 1.5h; Inert atmosphere; Microwave irradiation; Neat (no solvent); |
|
| 79% |
With N-Bromosuccinimide; triphenylphosphine In acetone at -18 - 80℃; for 1h; |
|
| 71% |
With dichlorido[1,3-diisopropylbenzimidazol-2-ylidene](η6-p-cymene)ruthenium(II) In neat (no solvent) at 130℃; for 18h; |
|
| 70% |
With Fe3O4/FeO In water at 40℃; for 2h; Green chemistry; |
General procedure for the N-alkylation reaction
General procedure: In a typical reaction, a suspension of amine (1.0 mmol) and alcohol (1.0 mmol) was added to a mixture of magnetic catalyst (0.04 g) with 1.5 ml distilled water. The resulting mixture was heated to 40 °C for an appropriate time under aerobic conditions. In the case of exposure by EMF, the resulting mixture was transferred to a Helmholtz cylinder permanent magnet and exposed with 362 μT intensity for an appropriate time. Progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, and the catalyst was separated from the product solution using an external magnet, washed with deoxygenated distilled water, dried in a desiccator at room temperature, and used for the next reaction cycle without any pre-treatment. Solvent of the reaction mixture was evaporated to generate the crude product. The product was concentrated and purifiedby column chromatography on silica-gel using EtOAc/heptane (1:4) as eluent. |
| 66% |
With (5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride; potassium carbonate In 1,3,5-trimethyl-benzene for 48h; Molecular sieve; Inert atmosphere; Reflux; |
|
| 65% |
With [IrCl(Cp*)(C13H15N2O3S)] In neat (no solvent) at 130℃; for 24h; Inert atmosphere; Schlenk technique; |
|
| 64% |
With (9-borabicyclo[3.3.1]nonanyl)ethyl(diphenyl)phosphine; palladium diacetate In toluene for 24h; Molecular sieve; Reflux; Inert atmosphere; |
Representative procedure for benzylation of amine with benzylic alcohol (Table 1, entry 3)
General procedure: Phosphine-borane ligand L1 (3.3 mg, 0.01 mmol), Pd(OAc)2 (2.3 mg, 0.01 mmol), and dried MS 4A (20 mg) were added in toluene (1.0 mL) under nitrogen. The mixture was stirred at room temperature during which it changed to a dark red suspension. To the suspension were added benzyl alcohol (1a, 216.3 mg, 2.0 mmol) and N-methylaniline (2a, 107.2 mg, 1.0 mmol). The progress of the reaction was monitored by TLC. After stirring in refluxing toluene for 24 h, the resulting suspension was concentrated and purified with column chromatography over silica gel (hexane/AcOEt = 95/5 v/v) to give 3aa (197.3 mg, 99%, Rf = 0.8; hexane/AcOEt = 80/20 v/v). |
| 60% |
With trimethylamine-N-oxide; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron In toluene at 20 - 135℃; Schlenk technique; Inert atmosphere; Molecular sieve; Sealed tube; |
|
| 55% |
With 1H-imidazole; iodine; chloro-diphenylphosphine In dichloromethane for 24h; Reflux; |
|
| 55% |
With potassium <i>tert</i>-butylate In toluene at 130℃; for 24h; Inert atmosphere; Sealed tube; |
|
| 52% |
With palladium nanoparticles embedded in the solid matrix of tetrabutylammonium bromide synthetized in supercritical carbon dioxide at 140℃; Sealed tube; Inert atmosphere; Green chemistry; |
3.3. General Procedure
General procedure: PdTBAB (1 mol % Pd in 250 mg of TBAB synthetized in scCO2), alcohol (2 mmol, 2 eq), amine (1 mmol, 1 eq) and anisole (1 mL) were introduced into a sealed tube under argon. The reaction was then heated at 140 °C for 12 h. After cooling the reaction at room temperature, the mixture was filtrated on Celite and washed with Et2O and the filtrate was concentrated under vacuum. The crude oil was purified by column chromatography. |
| 46% |
With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] at 160℃; for 1h; Inert atmosphere; Microwave irradiation; Sealed tube; neat (no solvent); |
|
| 75 %Spectr. |
With (o-(diphenylphosphino)aniline)Ru(CO)2Cl2; hydrogen; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate at 150℃; for 24h; |
|
| 78 %Spectr. |
With potassium dihydrogenphosphate; [IrCl(2,6-bis[2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine)] In neat (no solvent) at 140℃; for 24h; Inert atmosphere; Schlenk technique; |
|
| 99 %Chromat. |
With Ni nanoparticle-loaded θ-Al2O3 In o-xylene at 144℃; for 24h; Inert atmosphere; |
|
|
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; 1,3-bis-(diphenylphosphino)propane; potassium carbonate In toluene at 110℃; for 12h; Molecular sieve; Inert atmosphere; Schlenk technique; chemoselective reaction; |
2.3. N-alkylation reaction
General procedure: Ruthenium complex (0.015 mM), diphosphine ligand (0.07 mM), potassium carbonate (0.03 mM), and activated molecular sieves 3Å (0.1 g) were added to the reaction flask. The mixture was exposed to nitrogen for 10 min. Amine (1.0 mM), benzyl alcohol (1.0 mM), and dry toluene as solvent (1.0 mL) were added and refluxed for 12 h. After filtration, the reaction mixture was extracted three times with 5% hydrochloric acid solution, then the pH of the combined aqueous phase was adjusted to nine by the addition of dilute sodium hydroxide solution. The aqueous phase was extracted with dichloromethane and dried over MgSO4 prior to the injection to GC. |
| 94 %Chromat. |
With potassium hydroxide In toluene at 100℃; for 18h; Green chemistry; |
|
|
With (1S)-10-camphorsulfonic acid; dichloro[1-(4-tert-butylbenzyl)-3-(2-(1,3-dioxane-2-yl)ethyl)benzimidazole-2-ylidene](p-cymene)ruthenium(II) In toluene at 120℃; for 16h; Inert atmosphere; Schlenk technique; |
4.14. General procedure for catalytic N-Alkylation and N- and C(3) dialkylation of cyclic amines with alcohols
General procedure: As described in reference 35b and 38, to a stirred solution of cyclic amine (1 mmol) in 1 mL toluene was added D-(+)-camphorsulfonic acid (40 mol %). After stirring for 1 min, alcohol (2.5 mmol) and Ru-NHC (1 mol%) were added and stirred at 120 °C for 16 h. The reaction mixture was quenched in toluene and filtered through a short pad of SiO2. The filtrate was subjected to GC and GC-MS. All data reported are an average of at least two runs and, dodecane was used as internal standard. |
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