* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With potassium hydroxide In dimethyl sulfoxide at 120℃; Inert atmosphere
General procedure: A mixture of amine (2.0 mmol), aryl halides (1.0 mmol), catalyst (1.0 molpercent Pd), and DMSO (6 ml) was stirred for 16 h under nitrogen atmosphere at 120 ?C. The progress of reaction was monitored by gas chromatography. After completion, the reaction mixture was cooled and filtered to remove the catalyst which could be used for further reaction. The filtrate obtained was purified by flash column chromatography on silica gel to afford the desired product, which was confirmed by GC–MS. All the prepared compounds are known and compared with authentic samples.
83 %Chromat.
With C35H34N3OP2PdS(1+)*NO3(1-); sodium t-butanolate In 1,4-dioxane at 100℃; for 7 h;
General procedure: In a typical run, an oven-dried 10 ml round bottom flask was charged with a known mole percent of catalyst, NaOtBu (1.3 mmol), amine (1.2 mmol) and aryl halide (1 mmol) with the appropriate solvent(s) (4 ml). The flask was placed in a preheated oil bath at required temp. After the specified time the flask was removed from the oil bath, water (20 ml) was added, and extraction with ether (4×10 ml) was done. The combined organic layers were washed with water (3×10 ml), dried over anhydrous Na2SO4, and filtered. Solvent was removed under vacuum. The residue was dissolved in acetonitrile and analyzed by GC–MS.
Reference：
[1] Organometallics, 2012, vol. 31, # 21, p. 7336 - 7338
[2] Journal of Organic Chemistry, 2017, vol. 82, # 10, p. 5416 - 5423
[3] Journal of Molecular Catalysis A: Chemical, 2013, vol. 366, p. 321 - 332
[4] Angewandte Chemie - International Edition, 2016, vol. 55, # 42, p. 13219 - 13223[5] Angew. Chem., 2016, vol. 128, # 42, p. 13413 - 13417,5
[6] Journal of Organometallic Chemistry, 2010, vol. 695, # 21, p. 2284 - 2295
[7] Inorganica Chimica Acta, 2019, vol. 486, p. 232 - 239
2
[ 591-50-4 ]
[ 99-92-3 ]
[ 23600-83-1 ]
Yield
Reaction Conditions
Operation in experiment
53.4%
With copper; potassium carbonate In <i>N</i>-methyl-acetamide
368.1 1-(4-anilinophenyl)ethanone 4-amino-acetophenone (4.87 g; 36.0 mmol) is dissolved in dimethylformamide (75 ml). 15 g (0.108 mol) of potassium carbonate (previously dried at 170° C. under an argon atmosphere), 7.236 g (36.0 mmol) of iodobenzene, 0.4 g of copper in powder form and a catalytic quantity of copper iodide are added. The reaction mixture is taken to reflux for 12 hours. After leaving the reaction medium to return to ambient temperature, it is filtered on celite and poured into ice-cold water. After extraction with ethyl acetate, the organic phase is washed with water before being dried over magnesium sulphate, filtered and concentrated under vacuum. The product obtained is purified by crystallization from heptane in order to produce a yellow solid with a yield of 53.4percent. Melting point: 105° C.
With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; C40H43BN2P(1-)*C16H32LiO4(1+); potassium <i>tert</i>-butylate In tolueneInert atmosphere; Schlenk technique
General procedure: Typically, [Pd(cinnamyl)Cl]2 (0.0031 g, 0.006 mmol), ligand 1 (0.0107 mg, 0.012 mmol), and KO(t-Bu) (0.081 g, 0.72 mmol) were loaded into a Schlenk tube. If a solid aryl bromide or amine was used, it was also added at this time. To the mixture of solids, the aryl bromide (0.6 mmol) and amine (0.72 mmol) were added via syringe (if liquid), followed by toluene (2 mL). The resulting mixture was stirred at room temperature for 1 min., then placed in a pre-heated, 80 °C oil bath and allowed to react for 12 h. After this time, the mixture was removed from the bath and cooled to room temperature, diluted with EtOAc (5 mL), and filtered through silica (1 × 4 cm column, ~10 mL), eluting with EtOAc (20 mL) or until the filtrate ran clear. The volatiles were removed from the filtrate via rotary evaporation and the resulting residue was subjected to flash chromatography on silica gel (8 × 2 cm column, ~25 mL silica). Specific details related to the synthesis, yield and characterization of each coupled product are described below in Section 4.8.
84%
With potassium phosphate; copper(l) iodide In diethylene glycol at 70℃; for 14 h; Sealed tube
General procedure: A 10 mL vial was charged with CuI (9.5 mg, 0.05 mmol), PSAP (30 mg,0.05 mmol, > 100 mesh), K3PO4 (424 mg, 2 mmol), aryl bromides (1mmol), amines (1.5 mmol), DEG (2 mL), and a magnetic stir bar. The vessel was sealed with a septum and placed into a preheated oil batchat 70 °C. The reaction mixture was held at this temperature for 14 hours. After cooling to r.t., the reaction mixture was filtered, and the precipitates were thoroughly washed with water and EtOAc (3 × 20mL). The combined organic phases were washed with water and brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Theresidue was purified using flash column chromatography on silica gel(eluting with petroleum ether/EtOAc) to afford the desired products.
82%
With copper(l) iodide; tetrabutylammomium bromide; potassium hydroxide In water at 70℃; for 16 h; Green chemistry
General procedure: A 10 mL of vial was charged with CuI (10 mg, 0.05 mmol), PSP (0.25 mmol, size less than 90 μM), TBAB (40 mg, 0.25 mmol), base (1.0 mmol), aryl halides (0.5 mmol), arylamine (2.0 mmol), H2O (1.0 mL), and a magnetic stir bar. The vessel was sealed with a septum and placed into an oil bath, which was preheated to 70 °C (90 °C for alkyl amine, 120 °C for imidazole). The reaction mixture was stirred for another 16 h (8 h for imidazole). After allowing the mixture to cool to room temperature, the reaction mixture was filtrated, the precipitates were washed with water and ethyl acetate thoroughly. The filtrate was extracted with ethyl acetate (3×25 mL). The combined organic phases was washed with water and brine, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by flash column chromatograph on silica gel to afford the desired products.
80%
With C21H17N3O; copper; potassium hydroxide In propan-1-ol at 80℃; for 5 h; Sealed tube
The 198 mg (1mmol) 4 - bromophenylmethyl, 279 mg (3mmol) aniline, 64 mg (1mmol) Cu, 65.4 mg (0.2mmol) ligand L6, 56mg (1mmol) KOH, 2 ml propanol, adding 10 ml reaction tube, sealing, 80 °C reaction under the condition of 5h. After the stop of the reaction, water, extracted with ethyl acetate, washing, saturated salt water washing, after drying with anhydrous sodium sulfate, filtered, the filtrate is distilled under reduced pressure, purification by silica gel chromatography separation column column, shall be 1 - (4 - (phenylamino) phenyl) b one 169 mg, yield 80percent.
75%
With C104H96N16O8Pd2(4+)*4NO3(1-); sodium t-butanolate In toluene at 110℃; for 18 h;
General procedure: In a 50 mL round bottom flask, the mixture of iodobenzene (2 mmol), amine (2.4 mmol), t-BuONa (3 mmol), and 1 as catalyst (0.05 mol percent) was taken in toluene (10 mL). The reaction mixture was then heated to 110°C and continued for 12–18 h. The progress of the reaction was monitored by TLC. Upon completion of the reaction the aqueous reaction mixture was extracted with ethyl acetate, washed with brine, dried over MgSO4, concentrated, and purified by column chromatography on silica gel which afforded corresponding coupling products (yield 75–96percent).
53%
at 90℃; for 12 h; Sealed tube
General procedure: To a 10 mL sealed vial was added Cu(OAc)2·H2O (10 mg, 0.05mmol), N-methoxy-1H-pyrrole-2-carboxamide (7 mg, 0.05 mmol), aryl bromide (1.0 mmol), amine (3.0 mmol), K3PO4 (318 mg, 1.5 mmol),PEG-100 (2.0 g) and a magnetic stir bar. The reaction mixture was stirred in an oil bath preheated to 90 °C for 12 h. After allowing the mixture to cool to room temperature, the reaction mixture was extracted with ethyl acetate (3 × 25 mL) and water (20 mL). The combined organic phases were washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel to afford the desired product.
82 %Chromat.
at 150℃; for 12 h;
General procedure: In a typical run, an oven-dried 10 ml round bottom flask was charged with a known mole percent of catalyst, NaOtBu (1.3 mmol), amine (1.2 mmol) and aryl halide (1 mmol) with the appropriate solvent(s) (4 ml). The flask was placed in a preheated oil bath at required temp. After the specified time the flask was removed from the oil bath, water (20 ml) was added, and extraction with ether (4×10 ml) was done. The combined organic layers were washed with water (3×10 ml), dried over anhydrous Na2SO4, and filtered. Solvent was removed under vacuum. The residue was dissolved in acetonitrile and analyzed by GC–MS.
Reference：
[1] Journal of Organometallic Chemistry, 2017, vol. 841, p. 57 - 61
[2] Chemical Communications, 1998, # 15, p. 1509 - 1510
[3] Applied Organometallic Chemistry, 2011, vol. 25, # 5, p. 341 - 347
[4] Synthesis (Germany), 2018, vol. 50, # 19, p. 3911 - 3920
[5] Tetrahedron, 2013, vol. 69, # 42, p. 8974 - 8977
[6] Patent: CN106883132, 2017, A, . Location in patent: Paragraph 0053-0055
[7] Applied Organometallic Chemistry, 2017, vol. 31, # 11,
[8] European Journal of Organic Chemistry, 2010, # 17, p. 3219 - 3223
[9] Tetrahedron Letters, 2016, vol. 57, # 14, p. 1532 - 1536
[10] European Journal of Organic Chemistry, 2009, # 5, p. 635 - 642
[11] Angewandte Chemie - International Edition, 2016, vol. 55, # 42, p. 13219 - 13223[12] Angew. Chem., 2016, vol. 128, # 42, p. 13413 - 13417,5
[13] Russian Chemical Bulletin, 2012, vol. 61, # 5, p. 1009 - 1013[14] Izv. Akad. Nauk, Ser. Khim., 2012, vol. 61, # 5, p. 1004 - 1008,5
[15] Synthesis (Germany), 2014, vol. 46, # 24, p. 3356 - 3364
[16] Russian Journal of General Chemistry, 2005, vol. 75, # 2, p. 207 - 211
[17] Inorganica Chimica Acta, 2019, vol. 486, p. 232 - 239
4
[ 99-91-2 ]
[ 62-53-3 ]
[ 23600-83-1 ]
Yield
Reaction Conditions
Operation in experiment
81%
With sodium t-butanolate In toluene at 100℃; for 24 h;
In a pressure tube (obtainable, for example, from Aldrich), under an argon atmosphere, 1 mmol of aryl halide, 1.2 mmol of amine, 1.4 mmol of base, a suitable amount of carbene-Pd-olefin catalyst (1 mol percent) and 100 mg of diethylene glycol di-n-butyl ether (as an internal standard for the GC analysis) were added to 5 ml of toluene. The tube was sealed and suspended in a preheated silicone oil bath. After 24 h, it was allowed to cool to room temperature. The mixture was suspended in ether, and the supernatant solution was analysed by gas chromatography. The products may be isolated by distillation or column chromatography (silica gel, hexane/ethyl acetate mixtures).
77%
With NHC-Pd(II)-Im; potassium <i>tert</i>-butylate In toluene for 8 h; Inert atmosphere; Reflux
General procedure: Under N2 atmosphere, KOtBu (114.0 mg, 1.0 mmol), NHC-Pd(II)-Im complex 1 (5.2 mg, 1.0 mol percent), dry toluene (1.0 mL), chlorobenzene 2a (0.8 mmol), and aniline 3a (0.96 mmol) were successively added into a Schlenk reaction tube. The reaction mixture was stirred under reflux for 4 h. Then the solvent was removed under reduced pressure and the residue was purified by a flash chromatography on silica gel to give the pure product 4a.
66%
With (2-mesityl-1H-inden-3-yl)dicyclohexyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 1,2-dimethoxyethane at 120℃; for 24 h; Inert atmosphere
General procedure: Pd(dba)2/1-catalyzed amination of aryl halides: An oven-dried Schlenk tube equipped with a magnetic stirring bar was charged with Pd(dba)2 (5.8 mg, 0.010 mmol), ligand 1 (8.6 mg, 0.020 mmol) and tBuONa (134 mg, 1.4 mmol). The flask was capped with a rubber septum, evacuated, and then flushed with argon. This cycle was repeated three times. Amine (1.2 mmol), aryl halide (1.0 mmol) and DME (4 mL) were then successively added by syringe. The tube was stirred at room temperature for several minutes and then placed into a preheated oil bath (120 °C) for the time period as indicated in tables. After completion of reaction as judged by GC analysis, the reaction tube was allowed to cool to room temperature and the reaction mixture was adsorbed onto silica gel, and then purified by column chromatography (hexane/ethyl acetate as eluent) to afford the desired product.
23 %Chromat.
at 150℃; for 24 h;
General procedure: In a typical run, an oven-dried 10 ml round bottom flask was charged with a known mole percent of catalyst, NaOtBu (1.3 mmol), amine (1.2 mmol) and aryl halide (1 mmol) with the appropriate solvent(s) (4 ml). The flask was placed in a preheated oil bath at required temp. After the specified time the flask was removed from the oil bath, water (20 ml) was added, and extraction with ether (4×10 ml) was done. The combined organic layers were washed with water (3×10 ml), dried over anhydrous Na2SO4, and filtered. Solvent was removed under vacuum. The residue was dissolved in acetonitrile and analyzed by GC–MS.
Reference：
[1] European Journal of Organic Chemistry, 2015, vol. 2015, # 9, p. 2042 - 2050
[2] ACS Catalysis, 2018, vol. 8, # 7, p. 6606 - 6611
[3] Journal of Organic Chemistry, 2002, vol. 67, # 18, p. 6479 - 6486
[4] Patent: US2006/122398, 2006, A1, . Location in patent: Page/Page column 9
[5] Tetrahedron, 2012, vol. 68, # 10, p. 2414 - 2420
[6] Advanced Synthesis and Catalysis, 2011, vol. 353, # 1, p. 100 - 112
[7] Organic and Biomolecular Chemistry, 2017, vol. 15, # 27, p. 5805 - 5810
[8] European Journal of Organic Chemistry, 2011, # 24, p. 4523 - 4527
[9] Journal of Organometallic Chemistry, 2012, vol. 706-707, p. 99 - 105
[10] Applied Organometallic Chemistry, 2017, vol. 31, # 11,
[11] Chemistry - A European Journal, 2007, vol. 13, # 9, p. 2701 - 2716
[12] Patent: EP1894938, 2008, A1, . Location in patent: Page/Page column 60; 61; 62; 63
[13] Inorganica Chimica Acta, 2019, vol. 486, p. 232 - 239
5
[ 591-50-4 ]
[ 12775-96-1 ]
[ 99-92-3 ]
[ 23600-83-1 ]
Yield
Reaction Conditions
Operation in experiment
53.4%
With potassium carbonate In <i>N</i>-methyl-acetamide
335.1 1-(4-anilinophenyl)ethanone 4-amino-acetophenone (4.87 g; 36.0 mmol) is dissolved in dimethylformamide (75 ml). 15 g (0.108 mol) of potassium carbonate (previously dried at 170° C. under an argon atmosphere), 7.236 g (36.0 mmol) of iodobenzene, 0.4 g of copper powder and a catalytic quantity of copper iodide are added. The reaction mixture is taken to reflux for 12 hours. After leaving the reaction medium to return to ambient temperature, the latter is filtered on celite and poured into ice-cooled water. After extraction with ethyl acetate, the organic phase is washed with water before being dried over magnesium sulphate, filtered and concentrated under vacuum. The product obtained is purified by crystallization from heptane in order to produce a yellow solid with a yield of 53.4percent. Melting point: 105° C.
Reference：
[1] Journal of the Chemical Society, 1955, p. 1278,1280
[2] Bollettino Scientifico della Facolta di Chimica Industriale di Bologna, 1959, vol. 17, p. 33,37,41
[3] Bulletin de la Societe Chimique de France, 1969, p. 2342 - 2355
25
[ 99-92-3 ]
[ 23600-83-1 ]
Reference：
[1] Journal of the Chemical Society, 1955, p. 1278,1280
[2] Bollettino Scientifico della Facolta di Chimica Industriale di Bologna, 1959, vol. 17, p. 33,37,41
26
[ 118-91-2 ]
[ 23600-83-1 ]
Reference：
[1] Bollettino Scientifico della Facolta di Chimica Industriale di Bologna, 1959, vol. 17, p. 33,37,41
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