* 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 C26H22N3OPPdS; potassium acetate; silver(l) oxide In dichloromethane at 35℃; for 24 h; Schlenk technique; Inert atmosphere
A mixture of arylboronic acid (0.5 mmol), terminal alkyne oralkynyl carboxylic acid (0.6 mmol), DCM (2 mL), catalyst 3 (2 mol percent),Ag2O (1.0 mmol) and KOAc (1.0 mmol) in a Schlenk tube was stirredunder an argon atmosphere at 35 Cfor24h.TheexcessDCMwasthen removed by rotary evaporation and the residue was directlypuried by ash column chromatography (petroleum ether or pe-troleum ether/ethyl acetate) to afford the corresponding couplingproducts. 4.2.11. 4-(Phenylethynyl)benzaldehyde 32d(Table 1, entry 11) (99 mg,96percent yield). White solid, mp: 98e100C;1H NMR (400 MHz, CDCl3)d 9.99 (s, 1H), 7.84 (d, J7.8 Hz, 2H), 7.66 (d, J8.0 Hz, 2H), 7.56 (dd,J3.4, 2.9 Hz, 2H), 7.37 (s, 3H).13C NMR (100 MHz, CDCl3) d 191.6,135.3, 132.0, 131.7, 129.6, 128.9, 128.43, 128.41, 122.4, 93.5, 88.5.
93%
With nickel(II) (2-((3-methylthiophen-2-yl)methylene)hydrazinecarbothioamide)2.; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 5 h;
General procedure: In an oven-dried round-bottom flask, a mixture of arylboronic acid (1.0 mmol), phenylacetylene (1.2 mmol), complex 1 (5.0 molpercent), and 1,8-diazabicycloundec-7-ene(DBU) (2.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred at 100°C in air for 5 h. At the end of this time, the reaction mixture was diluted with EtOAc(20 mL) and washed with water (3 9 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and the solvent was stripped off under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixture to afford the desired product. The products were characterized by 1H and 13C NMR analysis.
Reference:
[1] Tetrahedron, 2014, vol. 70, # 35, p. 5980 - 5985
[2] Transition Metal Chemistry, 2017, vol. 42, # 7, p. 579 - 585
[3] Catalysis Science and Technology, 2014, vol. 4, # 5, p. 1276 - 1285
2
[ 1122-91-4 ]
[ 536-74-3 ]
[ 57341-98-7 ]
Yield
Reaction Conditions
Operation in experiment
100%
Stage #1: for 0.0833333 h; Sealed tube; Sonication Stage #2: for 3 h; Sealed tube
General procedure: In a tightly sealed tube (septa system),aryl halides (5.5 mmol) and 5percent nanocatalyst Pd/Cu, PPh3 (17 mg) were suspended in drytriethylamine (10 mL). The mixture was placed in an ultrasound bath and sonicated for 5 min.Then, the acetylene compound (5.6 mmol) was added and the mixture was stirred for 3 h. Themixture was cooled to room temperature and the catalyst was centrifuged, filtered and washedwith ethyl acetate (3 x 10 mL). The filtrate was washed three times with deionized water (3 x 15mL) and then dried over magnesium sulfate, filtered and concentrated under reduced pressureto give the product.
95%
With potassium phosphate; C30H37Br2N3Pd(2-) In dimethyl sulfoxide at 100℃; for 1 h;
General procedure: In a typical run, a 4 mL vial equipped with a magnetic stirrer bar was charged with a mixture of aryl halide (1 mmol), alkyne (2 mmol), Pd catalyst (0.01 mmol), K3PO4 (2 mmol), and 2 mL of DMSO in air. The mixture was stirred at 100 °C for 1 h, then cooled to room temperature and brine was added into it. The resulting mixture was extracted with ethyl acetate three times, and the crude product was obtained by removing the volatiles. The product was purified by flash column chromatography on silica gel.#10;
94%
With copper(l) iodide; C26H24N6NiS4; triethylamine In N,N-dimethyl-formamide at 80℃; for 8 h; Inert atmosphere
General procedure: In an oven-dried round bottom flask under an atmosphere of N2, a mixture of aryl halide (1 mmol), phenylacetylene (1.5 mmol), 1 (60.75 ppm or 0.05 molpercent), copper(I) iodide (5 mmol), and Et3N (3.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred 80 °C for 2 h. At the end of the mentioned time, the reaction mixture was diluted with EtOAc (20 mL), washed with water (3 x 10 mL). The combinedorganic layer was dried over anhydrous Na2SO4, filtered and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the desired product in high purity. The products were characterized by 1H and 13C NMR analysis. The procedure for the Sonogashira reaction of aryl bromides was similar as mentioned above in the case of aryl iodides, where aryl bromide (1 mmol) and 1 (121.5ppm or 0.1 mol percent) were used and the reaction was carried out for 8 h.
93%
With copper(l) iodide; C41H56ClNO4PdSe; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 15 h; Inert atmosphere
General procedure: A catalyst from 1-4 (10-2 M, 500 μL, 5 10-3 mmol, 0.5 molpercent) and (5 molpercent) of CuI were added to 3 mL degassed DMF taken in around bottom flask under nitrogen atmosphere. It was followed by the addition of aryl bromide (1.0 mmol), terminal alkyne (1.5 mmol) and K2CO3 (2.0 mmol). The reaction mixturewas heatedto 120 °C for 15 h under N2 atmosphere. Thereafter the mixture was cooled and extracted with ethyl acetate (15 mL). The extract was washed with water (10 mL) and dried over anhydrous Na2SO4. The solvent was evaporated with rotary evaporator and the resulting residue purified by a column chromatography on silica gel.
93%
With Cu[9,9-dimethyl-4,5-bis(diphenylphosphine)xanthene]I; palladium diacetate; caesium carbonate In N,N-dimethyl-formamide at 60℃; for 16 h; Inert atmosphere
General procedure: The mixture of aryl halides (1, 1.0 mmol) and alkynes (2, 1.2 mmol), Pd(OAc)2 (0.01mmol), Cu(Xantphos)I (0.01 mmol) and Cs2CO3 (2.0 mmol) in anhydrous DMF (5 mL) washeated at 60 oC for 16 h under argon atmosphere. After the reaction was finished, DMF was removed under reduced pressure. The mixture was extracted with ethyl acetate three times, then the combined organic layers were dried over anhydrous Na2SO4 and filtered. After removal of the solvent, the residue was purified by flash column chromatography on silica gel (hexane/ethyl acetate) to afford the pure product.
91%
With nickel(II) ferrite; potassium carbonate In water at 100℃; for 2.5 h;
General procedure: In a round-bottom flask equipped with a condenser for refluxingand a magnetic stirring bar, aryl/alkyl halide (1 mmol), phenylacetylene (1 mmol), K2CO3 (1.1 mmol), nickel ferrite nanoparticles(0.05 mmol) and water (3 ml) were added and heated at 100 °Cunder air atmosphere. The mixture was vigorously stirred underthese reaction conditions and its completion was monitored byTLC (EtOAc–n-hexane, 25:75).In each case, after completion of the reaction, the mixturewas dilutedwith diethyl ether and water. The organic layer was washed withbrine, dried over MgSO4, and concentrated under reduced pressureusing a rotary evaporator. The residue was purified by recrystallizationfrom ethanol and water.
91%
at 85℃; for 24 h; Inert atmosphere; Green chemistry
General procedure: To a mixture of the catalyst 3 (20mg containing 0.05molpercent Pd for aryl iodides and 40mg containing 0.1molpercent Pd for aryl bromides and chlorides), aryl halide (1mmol), alkyne (1.5mmol), and K2CO3 (1.5mmol, 207mg) was added PEG 200 (2mL) under argon atmosphere. The reaction mixture was stirred for the appropriate reaction time at 85 or 130°C (see, Table 2). The progress of the reaction was monitored by using gas chromatography. After completion of the reaction, pure products were obtained by using column chromatography with hexane and ethyl acetate as eluents.
90%
With C37H29ClN3PPdS; triethylamine In N,N-dimethyl-formamide at 20℃; for 12 h;
General procedure: In an oven-dried round bottom flask, a mixture of aryl halide (1 mmol), phenylacetylene (1.5 mmol), complex 1 (0.5 mol percent for aryl bromides, 1.0 mol percent for aryl chlorides) and Et3N (3.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred at room temperature (12 h for aryl bromides, 24 h for aryl chlorides). At the end of the time period mentioned, the reaction mixture was diluted with EtOAc (20 mL) and washed with water (3 x 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the desired product in high purity. The products were characterized by 1H and 13C NMR analysis.
90%
With sodium carbonate In 1-methyl-pyrrolidin-2-one; water at 60℃; for 1.05 h;
General procedure: To a mixture of phenyl acetylene (0.5 gm, 4.9 mmol), arylhalide (5.4 mmol) and Na2CO3 (5.4 mmol) in N-methyl2-pyrrolidone (NMP):Water, the DHOC-PdNps (0.0077mmol) were added. The reaction mixture was then stirredat 60 C (Table 3). The reaction was monitored by TLC,and after completion of the reaction, the reaction mixturewas cooled to room temperature. Then, the reaction mixture was extracted with ethyl acetate (60 mL 9 2) andwashed with water (60 mL). The organic phase waswashed with brine (50 mL), dried over Na2SO4, filtered and concentrated in vacuo. The products were purifiedusing 5 percent ethyl acetate in hexane as the eluent.
90%
With C31H24NO3PPd; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 5 h;
General procedure: A mixture of aryl halide (1mmol), alkyne (1mmol) were placed in a 25-mL round-bottomed flask, followed by addition of K2CO3 (1mmol) and palladium(II) complex (0.08molpercent) in DMF (5mL). The resulting mixture was stirred at 80°C for 5–7h. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature and the product was washed with water and extracted with ethyl acetate (3×10mL). The combined organic layers were dried over Na2SO4 and the solvent removed under reduced pressure to give crude product which was purified by column chromatography by using petroleum ether/ethyl acetate (4:1) as an eluent. The products were confirmed by 1H and 13C NMR.
88%
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 12 h; Green chemistry
General procedure: A mixture of aryl halide (1mmol), terminal alkyne (1mmol), K2CO3 (2mmol) and MNPFemTriazNHCAg complex (6) (100mg) in DMF (5mL) was stirred at 100°C. The progress of reaction was monitored by TLC. After completion, the reaction mixture was quenched in ice cold water and 6 was separated by external magnet. The reaction mixture was extracted with ethyl acetate (3×25mL). Evaporation of solvent in vaccuo followed by column chromatography over silica gel using petroleum ether/ethyl acetate afforded desired Sonogashira coupling products.
87%
With trans-{(1-ethyl-2-(4-bromophenyl)imidazol-3-ylidene[1,2-a]pyridine)}PdI2(pyridine); caesium carbonate In water; N,N-dimethyl-formamide at 90℃; for 3 h; Schlenk technique
General procedure: In a typical catalysis run, performed in air, a 25mL round bottom flask charged with a mixture of the aryl bromide or iodide, terminal alkyne, Cs2CO3, and diethyleneglycol-di-n-butyl ether (internal standard) in the molar ratio of 1:2:2:1. Palladium complexes (1–4)b, or PdCl2 or (COD)PdCl2 (4molpercent) was added to the mixture followed by 10mL solvent (DMF–H2O (7:3 v/v) and the reaction mixture was heated at 90°C for 3h, after which an aliquot was filtered and the product analyzed by gas chromatography using diethyleneglycol-di-n-butyl ether internal standard.
87%
With C59H51NO3P4Pd(2+)*3CF3O3S(1-); caesium carbonate In methanol at 60℃; for 24 h;
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene (1.3 mmol), Cat. (0.001 molpercent), Cs2CO3 (2.5 mmol), and methanol (3 ml) was heated to 60 °C for 24 h. The reaction mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The combined organic extracts were washed with brine and dried over CaCl2 and MgSO4. The solvent was evaporated and coupling product was obtained. The liquid residues were purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and the solid residues were purified by re-crystallization from ethanol and water.
85%
With [N-benzyl DABCO]+[Cu4Cl5]-; potassium carbonate In N,N-dimethyl-formamide at 135℃; for 3.5 h; Inert atmosphere
General procedure: Aryl halide (0.2 mmol) and K2CO3 (0.4 mmol) were added to a mixture of DMF (2 mL) and catalyst A (5 mol percent) in a round-bottom flask equipped with a condenser and under an N2 atmosphere. The mixture was heated in an oil bath at 135 °C and then phenylacetylene (0.22 mmol) was added in two portions. The mixture was stirred continuously during the reaction and monitored by thin-layer chromatography (TLC) and gas chromatography (GC). After the reaction was complete, the mixture was cooled to room temperature and diluted with EtOAc and H2O. The product was extracted with EtOAc and the organic phase dried over MgSO4, filtered, and concentrated. The arylalkynes obtained could be purified by silica gel column chromatography (hexane:EtOAc). The arylalkyne products were known compounds and were characterized from their IR, 1H NMR, and GC-MS.
85%
Stage #1: With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine In N,N-dimethyl-formamide at 20℃; for 0.25 h; Inert atmosphere Stage #2: With triethylamine In N,N-dimethyl-formamide at 20℃; for 0.5 h; Inert atmosphere Stage #3: at 80℃; for 12 h; Inert atmosphere
To a solution of 4-bromobenzaldehyde (500 mg, 2.70 mmol) in DMF (9 mL) was added Pd(PPh3)2Cl2 (14 mg, 0.02 mmol), PPh3 (10.5 mg, 0.04 mmol) and copper iodide (5mg) under argon atmosphere, and the suspension was stirred at room temperature for 15 min. Triethylamine (2 mL) was added to the reaction mixture. After stirring for 30 min at room temperature, phenylacetylene (306 mg, 3.0 mmol) was added. The reaction mixture was heated at 80 °C for 12 h and allowed to cool to room temperature. All volatile materials were removed in vacuum, and the residue was extracted with diethyl ether (3 × 10 mL). The crude product was purified using column chromatography (silica gel/ethyl acetate:petroleum ether 20:80) afforded 1 (472 mg, 85percent) as a light yellow solid.
85%
With potassium carbonate In ethanol; water at 90℃; for 0.583333 h; Microwave irradiation
General procedure: Into a 10 mL vial, aryl halide (1.0 mmol), phenylacetylene(1.2 mmol), K2CO3 (3.0 mmol), ethanol (3.0 mL), water (1.0 mL) and resin-PdNPs catalyst (300 mg) were taken and heated in a CEM microwave (150 w, 90°C) for different intervals of time (Scheme 6.1). The reaction was quenched in 10 mL cold water. The resulting solution was extracted with Et2O. The combined ether extract dried over anhydrous MgSO4 and solvent removed using a rotaevaporator. The crude product thus isolated was recrystallized from appropriate solvents.The effect of various parameters was studied taking coupling of iodobenzene and phenylacetylene as the standard reaction.
84%
With [PdCl2((C6H5)2PCH2P(C6H5)2CHC(O)C6H4NO2)]; potassium carbonate In N,N-dimethyl-formamide at 130℃; for 5 h;
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene(1.3 mmol), catalyst (0.001 mol percent), K2CO3 (2.5 mmol), and DMF(2 ml) was heated to 130 C. The mixture was then cooled to roomtemperature and the solvent was removed under reduced pressure.The combined organic extracts were washed with brine and driedover CaCl2 or MgSO4. The solvent was evaporated and liquid residueswere purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and solid residues were purified byrecrystallization from EtOH and H2O. Products were identified bycomparison of their 1H and 13C NMR spectral data those reportedin the literature.
81%
With copper(l) iodide; C31H26N4PPdS(1+)*Cl(1-); sodium hydroxide In ethanol; toluene at 110℃; for 17 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) andpalladium catalyst (a known molpercent) in an appropriate solvent(4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) wasadded and heated at required temp. After completion of the reaction(monitored by TLC), the flask was removed from the oil bathand water (20 mL) added, followed by extraction with ether(4 10 mL). The combined organic layers were washed with water(3 10 mL), dried over anhydrous Na2SO4, and filtered. Solventwas removed under vacuum. The residue was dissolved in hexaneand analyzed by GC–MS using Elite-5 columns, which are fused silicacapillary columns coated with 5percent diphenyl and 95percent dimethylpolysiloxane.
81%
With [(Pd{(κ2-C,N)-(3-(dimethylaminomethyl)indole)}µ-OAc)2]; potassium carbonate In water; N,N-dimethyl-formamide at 120℃; for 6 h;
General procedure: A 50-mL round-bottom flask was charged with aryl halide (1 mmol), phenylacetylene (1.5 mmol), K2CO3 (2 mmol), DMF:H2O (1:1) (4 mL), and the C,N-palladacycle (0.1 molpercent Pd). The mixture was stirred at 100°C for the desired reaction time. The reaction was monitored by GC. After the reaction was complete, the mixture was cooled to room temperature and diluted with EtOAc and H2O. The product was extracted with EtOAc and the organic phase dried over MgSO4, filtered, and concentrated. The arylalkynes obtained could be purified by silica gel column chromatography (hexane:EtOAc).The arylalkyne products were known compounds and were characterized from their 1H NMR and 13C NMR.
80%
at 60℃;
To a solution of 4-bromobenzaldehyde (250 mg, 1.35 mmol, 1.0 equiv.), PdCl2(PPh3)2 (19.0 mg, 27.0 prnol, 4 molpercent) and Cul (10.3 mg, 54.0 Mmol, 2 molpercent) in degassed NEt.3 (12 mL) was added phenylacetylene (180 mg, 1.76 mmol, 1.3 equiv.). The reaction was stirred at 60 °C over night and the solvent removed under reduced pressure. The crude material was purified by flash column chromatography (S1O2; petrolether : ethylacetate = 50:1 ), followed by recrystallization in ChteCte/pentane, to afford the title compound 1i as colorless solid (223 mg, 1.08 mmol, 80percent).
77%
With piperidine; [Pd{C6H4(CH2N(CH2Ph)2)}(μ-Br)]2 In 1-methyl-pyrrolidin-2-one at 100℃; for 0.133333 h; Microwave irradiation
General procedure: A mixture of the aryl halide (0.5 mmol), phenylacetylene(0.5 mmol), piperidine (1 mmol), ortho-palladated catalyst(0.2 mol percent) was added to NMP (3 mL) in round-bottom flask equipped with condenser and placed into the Milestone microwave. Initially using a microwave power of 600 W the temperature was ramped from room temperature to 100 °C and then held at this temperature until the reaction was completed. During this time, the power was modulated automatically to keep the reaction mixture at 100 °C. The mixture was stirred continuously during the reaction and monitored by both TLC and GC. After the reaction was complete, the mixture was cooled to room temperature and was diluted with n-hexane and water. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure using rotary evaporator. The residue was purified by silica gel column chromatography.
87 %Chromat.
With piperidine In water at 100℃; for 6 h;
General procedure: In a typical reaction, a mixture of aryl halides (1.0 mmol), phenylacetylene (1.5 mmol), piperidine (2.0 mmol), H2O (6 ml) and catalyst (0.5 molpercent of Pd) was stirred at 100 °C for appropriate time. Progress of the reaction was monitored by GC analysis at different time interval of the reaction. After the completion of the reaction, the mixture was cooled to room temperature, diluted with water, and extracted with CH2Cl2 for three times. The organic phase thuscollected was dried with Na2SO4 and concentrated. The crude product was purified by flash column chromatography on silica gel. The product was analyzed by GC/MS, 1H NMR and elemental analyses. All the products were known compounds and were identified by comparison of their physical and spectra data with those of authentic samples.
85 %Chromat.
With copper(l) iodide; C18H14N2Pd; sodium hydroxide In ethanol; toluene at 25℃; for 5 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) and palladium catalyst (a known molpercent) in 1:1 ethanol–toluene (4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) were added and heated at 25 °C. After completion of the reaction (monitored by TLC), the flask was removed from the oil bath and water (20 mL) added, followed by extraction with ether (4 × 10 mL). 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 hexane and analyzed by GC–MS.#10;
100 %Spectr.
at 100℃; for 5 h; Sealed tube
General procedure: In a tightly sealed tube (septa system), aryl halides (5.4 mmol), the catalyst, PPh3 and CuI (compare Table 2 and Table 3 for the exact mixture compositions) were suspended in dry triethylamine (10 mL). The mixture was placed in an ultrasound bath and sonicated for 5 min. Then, the acetylene compound (5.6 mmol) was added and the mixture was stirred as indicated in Table 2 and Table 3. The mixture was cooled to room temperature, and the catalyst was centrifuged, filtered, and washed with deionized water (2×10 mL) and ethyl acetate (2×10 mL). The filtrate was poured into 15 mL of dilute hydrochloric acid solution and the aqueous layer was extracted three times with dichloromethane (3×15 mL). The collected organic layer was washed with deionized water (15 mL) and then dried over magnesium sulfate, filtered, and concentrated under reduced pressure, affording the product. The conversion and selectivity were determined by 1H NMR spectroscopy. The spectra was recorded on a Bruker Avance (400MHz or 500MHz) using deuterated solvents: CDCl3 and DMSO with TMS as internal standard.
99 %Chromat.
With 1,4-diaza-bicyclo[2.2.2]octane In N,N-dimethyl acetamide at 60℃; for 24 h;
General procedure: Aryl halide and a terminal alkyne, with an equivalent molar ratioof 1.0–1.5, were added to a mixture of PdbisindoleSiO2Fe3O4(0.18 mmol, 20 mg) and DABCO (2.0 mmol, 224 mg) in a flask and2 mL DMA was added. The reaction mixture was stirred at 60C foraryl iodides and aryl bromides. The reaction temperature was setto 120C for aryl chlorides and 1 mmol TBAB was also added. Theprogress of the reaction was monitored by gas chromatography.After completion of the reaction, distilled water (2 mL) was addedto the reaction mixture and the crude product was extracted withethyl acetate (3 × 5.0 mL). The crude product was further purifiedby column chromatography using n-hexane and ethyl acetate as eluents.
100 %Chromat.
With C18H20BrClN2O2Pd2S2; sodium acetate In water; dimethyl sulfoxide at 110℃; for 24 h;
General procedure: A mixture of aryl halide (1.0 mmol), phenyl acetylene(1.5 mmol), precatalyst (2 molpercent), 2 mL solvent and 3 mmol basewas stirred under air atmosphere at 110 C for the desired timeuntil complete consumption of starting material as monitored byTLC. After the mixture was washed with water, extracted withethyl acetate (2 * 5 mL), dried over MgSO4, and injected to the GCchromatography. All of compounds have been characterized by1H NMR spectra.
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[67] Applied Organometallic Chemistry, 2014, vol. 28, # 9, p. 696 - 698
[68] RSC Advances, 2015, vol. 5, # 114, p. 94369 - 94374
[69] Green Chemistry, 2017, vol. 19, # 5, p. 1353 - 1361
[70] European Journal of Organic Chemistry, 2011, # 25, p. 4773 - 4787
[71] Journal of Organometallic Chemistry, 1975, vol. 93, p. 259 - 263
[72] Patent: EP1346993, 2003, A1,
[73] Advanced Synthesis and Catalysis, 2008, vol. 350, # 14-15, p. 2391 - 2400
[74] Journal of Organometallic Chemistry, 2009, vol. 694, # 21, p. 3477 - 3486
[75] European Journal of Inorganic Chemistry, 2009, # 12, p. 1608 - 1618
[76] Dalton Transactions, 2009, # 47, p. 10581 - 10591
[77] Dalton Transactions, 2011, vol. 40, # 1, p. 44 - 46
[78] Journal of Organometallic Chemistry, 2011, vol. 696, # 13, p. 2689 - 2692
[79] Journal of Molecular Catalysis A: Chemical, 2011, vol. 344, # 1-2, p. 62 - 73
[80] Journal of Organometallic Chemistry, 2013, vol. 736, p. 1 - 8
[81] Dalton Transactions, 2013, vol. 42, # 19, p. 6803 - 6809
[82] European Journal of Inorganic Chemistry, 2013, # 26, p. 4654 - 4661
[83] Journal of Catalysis, 2014, vol. 313, p. 1 - 8
[84] Catalysis Communications, 2013, vol. 40, p. 23 - 26
[85] Dalton Transactions, 2015, vol. 44, # 2, p. 725 - 732
[86] Chinese Journal of Catalysis, 2015, vol. 36, # 7, p. 1047 - 1053
[87] Chemical Communications, 2016, vol. 52, # 8, p. 1571 - 1574
[88] RSC Advances, 2016, vol. 6, # 58, p. 52656 - 52664
[89] Journal of Photochemistry and Photobiology A: Chemistry, 2016, vol. 326, p. 76 - 88
[90] Applied Catalysis A: General, 2016, vol. 525, p. 31 - 40
[91] New Journal of Chemistry, 2016, vol. 40, # 8, p. 6939 - 6945
[92] Inorganica Chimica Acta, 2016, vol. 451, p. 227 - 232
[93] RSC Advances, 2016, vol. 6, # 96, p. 93660 - 93672
[94] New Journal of Chemistry, 2017, vol. 41, # 12, p. 5105 - 5113
3
[ 104-88-1 ]
[ 536-74-3 ]
[ 57341-98-7 ]
Yield
Reaction Conditions
Operation in experiment
92%
With nickel(II) ferrite; potassium carbonate In water at 100℃; for 3 h;
General procedure: In a round-bottom flask equipped with a condenser for refluxingand a magnetic stirring bar, aryl/alkyl halide (1 mmol), phenylacetylene (1 mmol), K2CO3 (1.1 mmol), nickel ferrite nanoparticles(0.05 mmol) and water (3 ml) were added and heated at 100 °Cunder air atmosphere. The mixture was vigorously stirred underthese reaction conditions and its completion was monitored byTLC (EtOAc–n-hexane, 25:75).In each case, after completion of the reaction, the mixturewas dilutedwith diethyl ether and water. The organic layer was washed withbrine, dried over MgSO4, and concentrated under reduced pressureusing a rotary evaporator. The residue was purified by recrystallizationfrom ethanol and water.
91%
With 1,4-diaza-bicyclo[2.2.2]octane; tetrabutylammomium bromide In N,N-dimethyl acetamide at 120℃; for 48 h;
General procedure: Aryl halide and a terminal alkyne, with an equivalent molar ratioof 1.0–1.5, were added to a mixture of PdbisindoleSiO2Fe3O4(0.18 mmol, 20 mg) and DABCO (2.0 mmol, 224 mg) in a flask and2 mL DMA was added. The reaction mixture was stirred at 60C foraryl iodides and aryl bromides. The reaction temperature was setto 120C for aryl chlorides and 1 mmol TBAB was also added. Theprogress of the reaction was monitored by gas chromatography.After completion of the reaction, distilled water (2 mL) was addedto the reaction mixture and the crude product was extracted withethyl acetate (3 × 5.0 mL). The crude product was further purifiedby column chromatography using n-hexane and ethyl acetate as eluents.
80%
With C59H51BrOP4Pd(2+)*3CF3O3S(1-); caesium carbonate In methanol at 60℃; for 24 h;
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene (1.3 mmol), Cat. (0.001 molpercent), Cs2CO3 (2.5 mmol), and methanol (3 ml) was heated to 60 °C for 24 h. The reaction mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The combined organic extracts were washed with brine and dried over CaCl2 and MgSO4. The solvent was evaporated and coupling product was obtained. The liquid residues were purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and the solid residues were purified by re-crystallization from ethanol and water.
78%
With C37H29ClN3PPdS; triethylamine In N,N-dimethyl-formamide at 20℃; for 24 h;
General procedure: In an oven-dried round bottom flask, a mixture of aryl halide (1 mmol), phenylacetylene (1.5 mmol), complex 1 (0.5 mol percent for aryl bromides, 1.0 mol percent for aryl chlorides) and Et3N (3.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred at room temperature (12 h for aryl bromides, 24 h for aryl chlorides). At the end of the time period mentioned, the reaction mixture was diluted with EtOAc (20 mL) and washed with water (3 x 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the desired product in high purity. The products were characterized by 1H and 13C NMR analysis.
74%
With [PdCl2((C6H5)2PCH2P(C6H5)2CHC(O)C6H4NO2)]; potassium carbonate In N,N-dimethyl-formamide at 130℃; for 10 h;
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene(1.3 mmol), catalyst (0.001 mol percent), K2CO3 (2.5 mmol), and DMF(2 ml) was heated to 130 C. The mixture was then cooled to roomtemperature and the solvent was removed under reduced pressure.The combined organic extracts were washed with brine and driedover CaCl2 or MgSO4. The solvent was evaporated and liquid residueswere purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and solid residues were purified byrecrystallization from EtOH and H2O. Products were identified bycomparison of their 1H and 13C NMR spectral data those reportedin the literature.
72%
at 150℃; for 24 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) andpalladium catalyst (a known molpercent) in an appropriate solvent(4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) wasadded and heated at required temp. After completion of the reaction(monitored by TLC), the flask was removed from the oil bathand water (20 mL) added, followed by extraction with ether(4 10 mL). The combined organic layers were washed with water(3 10 mL), dried over anhydrous Na2SO4, and filtered. Solventwas removed under vacuum. The residue was dissolved in hexaneand analyzed by GC–MS using Elite-5 columns, which are fused silicacapillary columns coated with 5percent diphenyl and 95percent dimethylpolysiloxane.
69%
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 16 h; Green chemistry
General procedure: A mixture of aryl halide (1mmol), terminal alkyne (1mmol), K2CO3 (2mmol) and MNPFemTriazNHCAg complex (6) (100mg) in DMF (5mL) was stirred at 100°C. The progress of reaction was monitored by TLC. After completion, the reaction mixture was quenched in ice cold water and 6 was separated by external magnet. The reaction mixture was extracted with ethyl acetate (3×25mL). Evaporation of solvent in vaccuo followed by column chromatography over silica gel using petroleum ether/ethyl acetate afforded desired Sonogashira coupling products.
15 %Chromat.
With copper(l) iodide; C18H14N2Pd; sodium hydroxide In ethanol; toluene at 25℃; for 24 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) and palladium catalyst (a known molpercent) in 1:1 ethanol–toluene (4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) were added and heated at 25 °C. After completion of the reaction (monitored by TLC), the flask was removed from the oil bath and water (20 mL) added, followed by extraction with ether (4 × 10 mL). 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 hexane and analyzed by GC–MS.#10;
Reference:
[1] Catalysis Communications, 2014, vol. 60, p. 82 - 87
[2] Applied Catalysis A: General, 2016, vol. 525, p. 31 - 40
[3] RSC Advances, 2015, vol. 5, # 92, p. 75263 - 75267
[4] European Journal of Organic Chemistry, 2007, # 21, p. 3445 - 3448
[5] Catalysis Science and Technology, 2015, vol. 5, # 7, p. 3501 - 3506
[6] Catalysis Communications, 2013, vol. 37, p. 114 - 121
[7] Tetrahedron Letters, 2015, vol. 56, # 37, p. 5252 - 5256
[8] Journal of Fluorine Chemistry, 2008, vol. 129, # 11, p. 1124 - 1128
[9] Tetrahedron Letters, 2013, vol. 54, # 35, p. 4656 - 4660
[10] Inorganica Chimica Acta, 2015, vol. 425, p. 67 - 75
[11] Dalton Transactions, 2017, vol. 46, # 44, p. 15235 - 15248
[12] Dalton Transactions, 2017, vol. 46, # 38, p. 13065 - 13076
[13] Journal of Organometallic Chemistry, 2018, vol. 866, p. 112 - 122
[14] Tetrahedron Letters, 2006, vol. 47, # 18, p. 3023 - 3026
[15] Chemical Communications, 2002, # 8, p. 818 - 819
[16] New Journal of Chemistry, 2017, vol. 41, # 7, p. 2745 - 2755
[17] Organic and Biomolecular Chemistry, 2006, vol. 4, # 1, p. 111 - 115
[18] Journal of Organometallic Chemistry, 2013, vol. 736, p. 1 - 8
[19] European Journal of Inorganic Chemistry, 2013, # 26, p. 4654 - 4661
[20] Journal of Chemical Sciences, 2015, vol. 127, # 4, p. 597 - 608
4
[ 536-74-3 ]
[ 15164-44-0 ]
[ 57341-98-7 ]
Yield
Reaction Conditions
Operation in experiment
99%
With copper(l) iodide; C31H26N4PPdS(1+)*Cl(1-); sodium hydroxide In ethanol; toluene at 110℃; for 14 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) andpalladium catalyst (a known molpercent) in an appropriate solvent(4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) wasadded and heated at required temp. After completion of the reaction(monitored by TLC), the flask was removed from the oil bathand water (20 mL) added, followed by extraction with ether(4 10 mL). The combined organic layers were washed with water(3 10 mL), dried over anhydrous Na2SO4, and filtered. Solventwas removed under vacuum. The residue was dissolved in hexaneand analyzed by GC–MS using Elite-5 columns, which are fused silicacapillary columns coated with 5percent diphenyl and 95percent dimethylpolysiloxane.
96%
With C20H29Cl2N5O2Pd; potassium carbonate In ethanol at 80℃; for 2 h;
General procedure: A vial was charged with an aryl halide (0.1 mmol), an aryl or alkylacetylene(0.11 mmol), K2CO3 (0.15 mmol), palladium catalyst (0.05 mol percent), and EtOH(2 mL). The mixture was refluxed with stirring for 2 h. After this time, themixture was cooled and CH2Cl2–n-hexane (1:2, 2 mL) and H2O (2 mL) wereadded. The organic layer was separated, filtered through a small amount ofsilica gel and analyzed by GC–MS. The solvent was removed and the residueweighed and analyzed by 1H NMR.
96%
With copper(l) iodide; C26H24N6NiS4; triethylamine In N,N-dimethyl-formamide at 80℃; for 2 h; Inert atmosphere
General procedure: In an oven-dried round bottom flask under an atmosphere of N2, a mixture of aryl halide (1 mmol), phenylacetylene (1.5 mmol), 1 (60.75 ppm or 0.05 molpercent), copper(I) iodide (5 mmol), and Et3N (3.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred 80 °C for 2 h. At the end of the mentioned time, the reaction mixture was diluted with EtOAc (20 mL), washed with water (3 x 10 mL). The combinedorganic layer was dried over anhydrous Na2SO4, filtered and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the desired product in high purity. The products were characterized by 1H and 13C NMR analysis.
92.3%
With potassium phosphate; palladium In 2-methoxy-ethanol; water at 80℃; for 0.5 h;
Iodobenzene 2.04 g (0.01 mol), phenylacetylene 1.53 g (0.015 mol), potassium phosphate 4.22 g (0.02 mol) were added to a round bottom flask of 50mL capacity purged with nitrogen, equipped with stirrer, thermometer, reflux condenser, then methyl cellosolve / water (1: 1) 20 mL was weighed and added. Then, alkali aqueous solution 10.02g containing palladium nanoparticle catalysts from synthesized in Production Example 1 (Pd amount relative iodobenzene is 0.01 molpercent) was added and heated in an oil bath and heated to reflux for 8 hours at 80 . After completion of the reaction, adding toluene 15mL and water 10 mL, the organic layer was separated. The organic layer was concentrated with an evaporator, and the resulting concentrated residue purified by silica gel column chromatography to obtain the target compound
85%
With [PdCl2((C6H5)2PCH2P(C6H5)2CHC(O)C6H4NO2)]; potassium carbonate In N,N-dimethyl-formamide at 130℃; for 4 h;
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene(1.3 mmol), catalyst (0.001 mol percent), K2CO3 (2.5 mmol), and DMF(2 ml) was heated to 130 C. The mixture was then cooled to roomtemperature and the solvent was removed under reduced pressure.The combined organic extracts were washed with brine and driedover CaCl2 or MgSO4. The solvent was evaporated and liquid residueswere purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and solid residues were purified byrecrystallization from EtOH and H2O. Products were identified bycomparison of their 1H and 13C NMR spectral data those reportedin the literature.
78%
With bis(cyclohexylisocyanide)palladium(II) chloride; potassium carbonate; benzoic acid hydrazide In ethanol at 80℃; for 2 h;
General procedure: A solution of comple 1 in ethanol with a required concentrationwas added with stirring to a mixture of iodoarene2a–2g (0.3 mmol), phenylacetylene (3, 0.5 mmol),potassium carbonate (0.7 mmol), and ethanol (2 mL). The mixture was heated for 2 h on an oil bath at a bathtemperature of 80°C. After cooling to room temperature,the mixture was diluted with 10 mL of waterand extracted with hexane–methylene chloride (5 : 1,2 × 5 mL), and the combined extracts were dried overanhydrous sodium sulfate and analyzed by GC/MS.The solvent was evaporated, and the product wasisolated by silica gel column chromatography usingn-hexane as eluent.The properties of the isolated compounds were inagreement with the data given in [23–27].
74.4%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃;
1.1.23 Synthesis of compound 1.1.23 Step 1. Synthesis of 4-(phenylethynyl)benzaldehyde [1.1.23a] 1.1.23a To a degassed solution of ethynylbenzene (0.3 ml_, 2.73 mmol), 4-iodobenzaldehyde (761 mg, 3.28 mmol), and Et3N (0.757 mL, 5.46 mmol) in THF (Volume: 21.6 ml_), Pd(PPh3)2CI2 (96 mg, 0.137 mmol) and Cul (36.4 mg, 0.191 mmol) were added. After stirring at room temperature overnight, the reaction mixture was concentrated on to silica gel and purified by silica gel column chromatography (EtOAc/heptane, 0-50percent). Fractions containing product were collected. Pale yellow crystals crashed out, which were washed with pentane and heptane to afford 4-(phenylethynyl)benzaldehyde [1.1.23a] (419 mg, 74.4 percent yield). 1H NMR (400 MHz, CDCI3) δ ppm 7.30 - 7.44 (m, 3 H) 7.45 - 7.59 (m, 2 H) 7.62 - 7.73 (m, 2 H) 7.76 - 7.98 (m, 2 H) 10.02 (s, 1 H)
80 %Chromat.
With copper(l) iodide; C18H14N2Pd; sodium hydroxide In ethanol; toluene at 25℃; for 5 h;
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 molpercent) and palladium catalyst (a known molpercent) in 1:1 ethanol–toluene (4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) were added and heated at 25 °C. After completion of the reaction (monitored by TLC), the flask was removed from the oil bath and water (20 mL) added, followed by extraction with ether (4 × 10 mL). 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 hexane and analyzed by GC–MS.#10;
Reference:
[1] Inorganica Chimica Acta, 2015, vol. 425, p. 67 - 75
[2] Tetrahedron Letters, 2014, vol. 55, # 13, p. 2101 - 2103
[3] Tetrahedron Letters, 2016, vol. 57, # 44, p. 4893 - 4897
[4] Journal of Chemical Sciences, 2015, vol. 127, # 3, p. 425 - 431
[5] Patent: JP6084874, 2017, B2, . Location in patent: Paragraph 0102; 0106
[6] Organic and Biomolecular Chemistry, 2018, vol. 16, # 15, p. 2748 - 2752
[7] European Journal of Organic Chemistry, 2008, # 31, p. 5244 - 5253
[8] Green Chemistry, 2015, vol. 17, # 2, p. 1071 - 1076
[9] Dalton Transactions, 2017, vol. 46, # 38, p. 13065 - 13076
[10] Tetrahedron Letters, 2013, vol. 54, # 35, p. 4656 - 4660
[11] Applied Organometallic Chemistry, 2018, vol. 32, # 12,
[12] Russian Journal of General Chemistry, 2017, vol. 87, # 8, p. 1663 - 1666[13] Zh. Obshch. Khim., 2017, vol. 87, # 8, p. 1247 - 1251,5
[14] Patent: WO2014/160649, 2014, A1, . Location in patent: Page/Page column 88-89
[15] RSC Advances, 2017, vol. 7, # 34, p. 21036 - 21044
[16] ACS Catalysis, 2016, vol. 6, # 6, p. 3771 - 3783
[17] Chemistry - An Asian Journal, 2017, vol. 12, # 17, p. 2221 - 2230
[18] European Journal of Inorganic Chemistry, 2011, # 21, p. 3174 - 3182
[19] Transition Metal Chemistry, 2010, vol. 35, # 3, p. 305 - 313
[20] Journal of Organometallic Chemistry, 2013, vol. 736, p. 1 - 8
[21] Journal of Organic Chemistry, 2015, vol. 80, # 13, p. 6922 - 6929
[22] Organic Letters, 2018, vol. 20, # 18, p. 5573 - 5577
5
[ 1719-19-3 ]
[ 104-88-1 ]
[ 57341-98-7 ]
Yield
Reaction Conditions
Operation in experiment
86%
With tetrabutylammomium bromide; potassium carbonate; palladium dichloride; XPhos In water at 120℃; Inert atmosphere; Schlenk technique; Green chemistry
General procedure: To a 25-mL Schlenk tube equipped with magnetic stir bar, aryl chloride (0.2 mmol), aryl propargylic alcohol (0.3 mmol), K2CO3 (2.0 equiv.), TBAB (1.0 equiv.), PdCl2 (2 molpercent), and Xphos (4 molpercent) were added in turn, then 2 mL H2O was added, and then the solution was refluxed for 24 h under N2 atmosphere. After the reaction was completed, the mixture was extracted with EtOAc or CH2Cl2. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The crude product was purified by flash chromatography on silica gel using hexane/ethyl acetate as the eluent to afford the desired product.
With nickel(II) (2-((3-methylthiophen-2-yl)methylene)hydrazinecarbothioamide)2.; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 5 h;
General procedure: In an oven-dried round-bottom flask, a mixture of arylboronic acid (1.0 mmol), phenylacetylene (1.2 mmol), complex 1 (5.0 molpercent), and 1,8-diazabicycloundec-7-ene(DBU) (2.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred at 100°C in air for 5 h. At the end of this time, the reaction mixture was diluted with EtOAc(20 mL) and washed with water (3 9 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and the solvent was stripped off under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixture to afford the desired product. The products were characterized by 1H and 13C NMR analysis.
Reference:
[1] Transition Metal Chemistry, 2017, vol. 42, # 7, p. 579 - 585
7
[ 1122-91-4 ]
[ 2170-06-1 ]
[ 57341-98-7 ]
Reference:
[1] Advanced Synthesis and Catalysis, 2006, vol. 348, # 15, p. 2101 - 2113
8
[ 591-50-4 ]
[ 63697-96-1 ]
[ 57341-98-7 ]
Yield
Reaction Conditions
Operation in experiment
76%
at 35 - 40℃; Inert atmosphere
General procedure: A mixture of PdCl2(PPh3)2 (11 mg, 0.016 mmol, 0.01 equiv), Et3N (4.7 mL, 34 mmol), 4-ethynylbenzaldehyde (1e)4f,g (201 mg, 1.55 mmol, 1.0 equiv), and iodobenzene derivative (1.63 mmol) was stirred at room temperature for 5 min; CuI (6 mg, 0.03 mmol, 0.02 equiv) was added and the mixture was stirred at 35-40 °C for 17-24 h under an argon atmosphere.4e After being cooled to room temperature, the mixture was diluted with EtOAc and washed with brine. The organic layer was dried over MgSO4, filtered, concentrated, and purified by flash column chromatography to afford 2.
With copper (I) iodide; C31H26N4PPdS(1+)*Cl(1-); sodium hydroxide In ethanol; toluene at 110℃; for 14h;
2.5.3. General procedure for Sonogashira coupling reactions
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 mol%) andpalladium catalyst (a known mol%) in an appropriate solvent(4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) wasadded and heated at required temp. After completion of the reaction(monitored by TLC), the flask was removed from the oil bathand water (20 mL) added, followed by extraction with ether(4 10 mL). The combined organic layers were washed with water(3 10 mL), dried over anhydrous Na2SO4, and filtered. Solventwas removed under vacuum. The residue was dissolved in hexaneand analyzed by GC-MS using Elite-5 columns, which are fused silicacapillary columns coated with 5% diphenyl and 95% dimethylpolysiloxane.
97%
With (Fe3O4 nanoparticles)(at)PEG/Cu-Co In water monomer at 80℃; for 3h; Green chemistry;
96%
With C20H29Cl2N5O2Pd; potassium carbonate In ethanol at 80℃; for 2h;
General procedure for the coupling of aryl halides with terminal acetylenes
General procedure: A vial was charged with an aryl halide (0.1 mmol), an aryl or alkylacetylene(0.11 mmol), K2CO3 (0.15 mmol), palladium catalyst (0.05 mol %), and EtOH(2 mL). The mixture was refluxed with stirring for 2 h. After this time, themixture was cooled and CH2Cl2-n-hexane (1:2, 2 mL) and H2O (2 mL) wereadded. The organic layer was separated, filtered through a small amount ofsilica gel and analyzed by GC-MS. The solvent was removed and the residueweighed and analyzed by 1H NMR.
96%
With copper (I) iodide; C26H24N6NiS4; triethylamine In N,N-dimethyl-formamide at 80℃; for 2h; Inert atmosphere;
Typical procedure for the Sonogashira reaction of aryl iodides with phenylacetylene
General procedure: In an oven-dried round bottom flask under an atmosphere of N2, a mixture of aryl halide (1 mmol), phenylacetylene (1.5 mmol), 1 (60.75 ppm or 0.05 mol%), copper(I) iodide (5 mmol), and Et3N (3.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred 80 °C for 2 h. At the end of the mentioned time, the reaction mixture was diluted with EtOAc (20 mL), washed with water (3 x 10 mL). The combinedorganic layer was dried over anhydrous Na2SO4, filtered and stripped off the solvent under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixtures to afford the desired product in high purity. The products were characterized by 1H and 13C NMR analysis.
96%
With Cu(II)IL/Schiff base complex decorated on γ-Fe2O3 In dimethyl sulfoxide at 90℃; for 3h;
General procedure for Sonogashira cross-couplingreaction
General procedure: In a typical run, 4-iodotoluene (1.0 mmol) and phenylacetylene(1.2 mmol) were dissolved in 2.0 mL DMSO.The catalyst (80 mg, 0.4 mol%) was added to the mixture,and the resultant mixture was stirred at 90 °C under aerobic conditions. The reaction progress was monitored byTLC. Upon the reaction completion, the magnetic catalystwas separated using an external magnetic field, and then,water (5 mL) and dichloromethane (5 mL) were addedto the reaction mixture. The organic layer was separated,and the aqueous layer was extracted with further DCM.The organic layers were combined, dried over MgSO4,andthen, the solvent was removed under reduced pressure. The products were purified by silica gel column chromatography.The products were identified by 1HNMR and 13CNMRand comparison with the corresponding authentic samples
95%
With potassium carbonate In ethanol at 78℃; for 7.5h;
92.3%
With tripotassium phosphate tribasic; palladium In 2-methoxy-ethanol; water monomer at 80℃; for 0.5h;
9
Iodobenzene 2.04 g (0.01 mol), phenylacetylene 1.53 g (0.015 mol), potassium phosphate 4.22 g (0.02 mol) were added to a round bottom flask of 50mL capacity purged with nitrogen, equipped with stirrer, thermometer, reflux condenser, then methyl cellosolve / water (1: 1) 20 mL was weighed and added. Then, alkali aqueous solution 10.02g containing palladium nanoparticle catalysts from synthesized in Production Example 1 (Pd amount relative iodobenzene is 0.01 mol%) was added and heated in an oil bath and heated to reflux for 8 hours at 80 . After completion of the reaction, adding toluene 15mL and water 10 mL, the organic layer was separated. The organic layer was concentrated with an evaporator, and the resulting concentrated residue purified by silica gel column chromatography to obtain the target compound
92%
With copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 80℃; for 15h; Green chemistry;
91%
With 1,4-diaza-bicyclo[2.2.2]octane In N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere;
2.8 General procedure for the Sonogashira-Hagihara reaction
General procedure: To a flask containing the aryl halide (0.5mmol) and phenylacetylene (0.75mmol, 0.08mL), DABCO (0.75mmol, 0.08g) and DMF (2mL), MWCNTIL-Pd nanocatalyst (25mg containing 0.5 mol% Pd) were added. The mixture was stirred at 80°C for aryl iodides and 100°C for aryl bromides under an argon atmosphere. After completion of the reaction (monitored by GC), deionized water (2mL) was added to the reaction mixture and the crude product was extracted with ethyl acetate (3×5mL). For further purification, the organic solvent was removed under vacuum and the resulting residue was purified by column chromatography on silica gel using hexane and ethyl acetate as eluents.
91%
With 1,4-diaza-bicyclo[2.2.2]octane In N,N-dimethyl-formamide at 80℃; for 10h; Inert atmosphere;
2.8 General procedure for the Sonogashira-Hagihara reaction
General procedure: To a flask containing the aryl halide (0.5mmol) and phenylacetylene (0.75mmol, 0.08mL), DABCO (0.75mmol, 0.08g) and DMF (2mL), MWCNTIL-Pd nanocatalyst (25mg containing 0.5 mol% Pd) were added. The mixture was stirred at 80°C for aryl iodides and 100°C for aryl bromides under an argon atmosphere. After completion of the reaction (monitored by GC), deionized water (2mL) was added to the reaction mixture and the crude product was extracted with ethyl acetate (3×5mL). For further purification, the organic solvent was removed under vacuum and the resulting residue was purified by column chromatography on silica gel using hexane and ethyl acetate as eluents.
90%
With copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 50℃; for 6h;
90%
With 1,4-diaza-bicyclo[2.2.2]octane; palladium(0) at 60℃; for 2.5h; Inert atmosphere; Green chemistry;
89%
With dimethylammonium chloride; potassium carbonate In glycerol at 120℃; for 8h;
Typical method for the Sonogashira coupling reaction
General procedure: A mixture of phenylacetylene (1.2 mmol), aryl halide (1 mmol), K2CO3 (2 mmol), and GO-Fe3O4-Cellulose-Pd (1 mol%, 0.024 g) in 3 mL of DES (DMAC:Gly) was left under stirring at 120 °C. After completing the reaction (monitored by TLC), the mixture was quenched with water (10 mL) and extracted with ethyl acetate (3 × 10 mL). The work-up procedure was performed similar to the Heck coupling reaction.
88%
With sodium hydroxide In water monomer at 60℃; for 1.08333h; Green chemistry;
88%
With copper (I) iodide; N,N-diisopropylamine In tetrahydrofuran at 20℃; for 24h;
86%
With copper (I) iodide; C36H38Cl6N6Pd3S2; potassium carbonate In dimethyl sulfoxide at 110℃; for 6h; Inert atmosphere;
85%
With [PdCl2((C6H5)2PCH2P(C6H5)2CHC(O)C6H4NO2)]; potassium carbonate In N,N-dimethyl-formamide at 130℃; for 4h;
General experimental procedure for the Sonogashira crosscoupling
General procedure: A mixture of an aryl halide (1 mmol), phenylacetylene(1.3 mmol), catalyst (0.001 mol %), K2CO3 (2.5 mmol), and DMF(2 ml) was heated to 130 C. The mixture was then cooled to roomtemperature and the solvent was removed under reduced pressure.The combined organic extracts were washed with brine and driedover CaCl2 or MgSO4. The solvent was evaporated and liquid residueswere purified by silica gel column chromatography (n-hexane:EtOAc, 80:20) and solid residues were purified byrecrystallization from EtOH and H2O. Products were identified bycomparison of their 1H and 13C NMR spectral data those reportedin the literature.
82%
With potassium carbonate In dimethyl sulfoxide at 110℃; for 4h;
78%
With bis(cyclohexylisocyanide)palladium(II) chloride; potassium carbonate; benzoic acid hydrazide In ethanol at 80℃; for 2h;
Sonogashira reaction (general procedure).
General procedure: A solution of comple 1 in ethanol with a required concentrationwas added with stirring to a mixture of iodoarene2a-2g (0.3 mmol), phenylacetylene (3, 0.5 mmol),potassium carbonate (0.7 mmol), and ethanol (2 mL). The mixture was heated for 2 h on an oil bath at a bathtemperature of 80°C. After cooling to room temperature,the mixture was diluted with 10 mL of waterand extracted with hexane-methylene chloride (5 : 1,2 × 5 mL), and the combined extracts were dried overanhydrous sodium sulfate and analyzed by GC/MS.The solvent was evaporated, and the product wasisolated by silica gel column chromatography usingn-hexane as eluent.The properties of the isolated compounds were inagreement with the data given in [23-27].
74.4%
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃;
1.1.23.1 Synthesis of 4-(phenylethynyl)benzaldehyde [1.1.23a]
1.1.23 Synthesis of compound 1.1.23 Step 1. Synthesis of 4-(phenylethynyl)benzaldehyde [1.1.23a] 1.1.23a To a degassed solution of ethynylbenzene (0.3 ml_, 2.73 mmol), 4-iodobenzaldehyde (761 mg, 3.28 mmol), and Et3N (0.757 mL, 5.46 mmol) in THF (Volume: 21.6 ml_), Pd(PPh3)2CI2 (96 mg, 0.137 mmol) and Cul (36.4 mg, 0.191 mmol) were added. After stirring at room temperature overnight, the reaction mixture was concentrated on to silica gel and purified by silica gel column chromatography (EtOAc/heptane, 0-50%). Fractions containing product were collected. Pale yellow crystals crashed out, which were washed with pentane and heptane to afford 4-(phenylethynyl)benzaldehyde [1.1.23a] (419 mg, 74.4 % yield). 1H NMR (400 MHz, CDCI3) δ ppm 7.30 - 7.44 (m, 3 H) 7.45 - 7.59 (m, 2 H) 7.62 - 7.73 (m, 2 H) 7.76 - 7.98 (m, 2 H) 10.02 (s, 1 H)
70%
With copper (I) iodide; palladium diacetate; metformin hydrochloride; potassium carbonate In water monomer at 100℃; for 8h; Inert atmosphere; Green chemistry;
65%
With potassium carbonate In ethanol; water monomer at 20℃; for 9h; Irradiation;
64%
With potassium carbonate In ethanol at 100℃; for 4h; Sealed tube; Inert atmosphere; Green chemistry;
With potassium carbonate In ethanol; N,N-dimethyl-formamide at 80℃;
With copper (I) iodide; triethylamine In water monomer at 70℃; for 8h;
80 %Chromat.
With copper (I) iodide; C18H14N2Pd; sodium hydroxide In ethanol; toluene at 25℃; for 5h;
4.5 General procedure for Sonogashira coupling reactions
General procedure: To slurry of aryl halide (1 mmol), cuprous iodide (10 mol%) and palladium catalyst (a known mol%) in 1:1 ethanol-toluene (4 mL), phenylacetylene (1.2 mmol) and NaOH (1.7 mmol) were added and heated at 25 °C. After completion of the reaction (monitored by TLC), the flask was removed from the oil bath and water (20 mL) added, followed by extraction with ether (4 × 10 mL). 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 hexane and analyzed by GC-MS.
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In acetonitrile at 20℃; for 16h;
Stage #1: p-(iodophenyl)carboxaldehyde With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 0.166667h; Schlenk technique;
Stage #2: ethynylbenzene at 20℃; Inert atmosphere; Schlenk technique;
9 %Chromat.
With dichloro(4,7-di(4',4''-difluoro-1',3',5',7'-tetramethyl-4'-bora-3'a,4'a-diaza-s-indacene)-1,10-phenanthroline)palladium(II); triethylamine; triphenylphosphine In N,N-dimethyl-formamide at 25℃; for 24h; Schlenk technique; Inert atmosphere; Irradiation;
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In dimethyl sulfoxide at 50℃; for 4h; Schlenk technique; Inert atmosphere;
With potassium carbonate In ethanol; water monomer at 100℃;
98 %Chromat.
With 1,4-diaza-bicyclo[2.2.2]octane In N,N-dimethyl acetamide at 30℃; for 24h; Inert atmosphere;
2.5 General procedure for Sonogashira-Hagihara reaction
General procedure: In a 5mL flask, ZIF-67PdCu (25mg) ArX (0.5mmol) and DABCO (0.75mmol) were well dispersed in 2mL of DMA under argon atmosphere. The aryl acetylene (0.75mmol) was added to the resulting mixture and stirred at 30°C for ArI and 40°C for ArBr for 24h. The progress of the reaction was monitored by TLC and GC. After completion of the reaction, the mixture was extracted with ethyl acetate (3×5mL) and water (10mL). The residue was purified by column and plate chromatography with hexane and ethyl acetate as eluents. All products were identified by 1HNMR and 13CNMR spectroscopy.
In diphenylether for 6h; Inert atmosphere; Reflux;
1.5.1-(4-Formylphenyl)-2,3,4,5,6-pentaphenylbenzene (2)
Tetraphenylcyclopentadienone (2.00 g, 5.20 mmol) and 4-phenylethynylbenzaldehyde (1) (1.07 g, 5.20 mmol) were combined in diphenyl ether (6 mL), and the mixture was heated at reflux for 6 h. The mixture was allowed to cool to room temperature, and the resulting white crystalline precipitate was separated by filtration and washed with ethanol and hexanes. Recrystallization from toluene yielded 1-(4-formylphenyl)-2,3,4,5,6-pentaphenylbenzene (2) (2.16 g, 74%) as a colorless solid.
64%
In diphenylether at 260℃; for 36h; Inert atmosphere;
64%
In diphenylether for 36h; Inert atmosphere; Reflux;
2.3.2. Synthesis of 1-formyl-(penta-phenylphenyl)benzene (HPB-CHO)
In a round-bottom flask, tetraphenylcyclopentadienone (460 mg, 1.2 mmol) and 1-formyldiphenylacetylene (247 mg, 1.2 mmol) were added to diphenylether (6 mL) and the whole reaction mixture was refluxed for 36 h under nitrogen atmosphere. Upon comple- tion of the reaction, the purple color faded to brown, then the reaction mixture was cooled at room temperature. With drop- wise addition of methanol, the solid product was precipitated, filtered under suction, and was purified by column chromatography. Physical state: off-white solid; 64% yield; Rf = 0.67 (1:9 ethyl ac- etate/hexane); mp > 250 °C; 1 H NMR (400 MHz, CDCl 3 -D) = 9.78 (s, 1H, CHO), 7.42 (d, 2H, Ar), 7.11 (d, 2H, Ar), 6.91 (m, 25H, Ar); 13 C NMR (400 MHz, CDCl 3 -D) : 191.0, 134.3, 130.4, 129.2, 127.6; ESI-MS; 562.23.
60%
In neat (no solvent) at 240℃; for 0.5h; Schlenk technique; Inert atmosphere; Microwave irradiation;
Step 1 :Similar procedures described in WO 02/09705 & WO 02/09706 To a solution of 4-(phenylethynyl)benzaldehyde (2.8 g, 13.6 mmol, 1 eq) in MeCN (240 ml) was added (S)-2-mercaptosuccinic acid (6. 2 g, 40.8 mmol, 3 eq) and 3- aminobenzamide (1.85 g, 13.6 mmol, 1 eq). The reaction was stirred at 83C for 3 days. The reaction was cooled and filtered to give solid. The solid was adjusted PH= 8~9 with saturated Na2C03 and extracted with ethyl acetate (50 ml* 3). The water phase was adjusted PH=3~4 with 4N HCI and filtered to give solid. The solid was washed with EtOH (10 ml) and MeCN (10 ml) to afford title compound as a light yellow solid (3 g, 51.7%).
51.7%
With hydrogenchloride; In acetonitrile; at 83℃; for 72h;
Step 1 Similar procedures described in WO 02/09705 & WO 02/09706 To a solution of 4-(phenylethynyl)benzaldehyde (2.8 g, 13.6 mmol, 1 eq) in MeCN (240 ml) was added (S)-2-mercaptosuccinic acid (6.12 g, 40.8 mmol, 3 eq) and <strong>[3544-24-9]3-aminobenzamide</strong> (1.85 g, 13.6 mmol, 1 eq). The reaction was stirred at 83 C. for 3 days. The reaction was cooled and filtered to give solid. The solid was adjusted PH=8?9 with saturated Na2CO3 and extracted with ethyl acetate (50 ml*3). The water phase was adjusted PH=3?4 with 4N HCl and filtered to give solid. The solid was washed with EtOH (10 ml) and MeCN (10 ml) to afford title compound as a light yellow solid (3 g, 51.7%).
With C26H22N3OPPdS; potassium acetate; silver(l) oxide In dichloromethane at 35℃; for 24h; Schlenk technique; Inert atmosphere;
4.2.11. 4-(Phenylethynyl)benzaldehyde
A mixture of arylboronic acid (0.5 mmol), terminal alkyne oralkynyl carboxylic acid (0.6 mmol), DCM (2 mL), catalyst 3 (2 mol %),Ag2O (1.0 mmol) and KOAc (1.0 mmol) in a Schlenk tube was stirredunder an argon atmosphere at 35 Cfor24h.TheexcessDCMwasthen removed by rotary evaporation and the residue was directlypuried by ash column chromatography (petroleum ether or pe-troleum ether/ethyl acetate) to afford the corresponding couplingproducts. 4.2.11. 4-(Phenylethynyl)benzaldehyde 32d(Table 1, entry 11) (99 mg,96% yield). White solid, mp: 98e100C;1H NMR (400 MHz, CDCl3)d 9.99 (s, 1H), 7.84 (d, J7.8 Hz, 2H), 7.66 (d, J8.0 Hz, 2H), 7.56 (dd,J3.4, 2.9 Hz, 2H), 7.37 (s, 3H).13C NMR (100 MHz, CDCl3) d 191.6,135.3, 132.0, 131.7, 129.6, 128.9, 128.43, 128.41, 122.4, 93.5, 88.5.
93%
With nickel(II) (2-((3-methylthiophen-2-yl)methylene)hydrazinecarbothioamide)2.; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 5h;
Procedure for the oxidative coupling reaction
General procedure: In an oven-dried round-bottom flask, a mixture of arylboronic acid (1.0 mmol), phenylacetylene (1.2 mmol), complex 1 (5.0 mol%), and 1,8-diazabicycloundec-7-ene(DBU) (2.0 mmol) in DMF (5 mL) was taken. The reaction mixture was stirred at 100°C in air for 5 h. At the end of this time, the reaction mixture was diluted with EtOAc(20 mL) and washed with water (3 9 10 mL). The organic layer was dried over anhydrous Na2SO4, filtered and the solvent was stripped off under reduced pressure. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixture to afford the desired product. The products were characterized by 1H and 13C NMR analysis.
92%
With anthracen-9-ylmethylene-(4-methoxyphenyl)amine; palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 2.5h;
Typical procedure fortheoxidative coupling reaction
General procedure: A mixture of arylboronic acid (1.0mmol), phenylacety-lene (1.2mmol), Pd(OAc) 2 (1.0mol%), L (1.0mol%) and 1,8-diazabicycloundec-7-ene (DBU) (2.0mmol) in DMF (5mL) was stirred at 100°C in air for 4h. The reaction mixture was then diluted with EtOAc (20mL) and washed with water (3 × 10mL). The organic layer was dried over anhydrous Na 2 SO 4 , filtered and the solvent was removed. The residue was subjected to column chromatography on silica gel using ethyl acetate and n-hexane mixture to afford the desired product. The products were characterized by 1 H and 13 C NMR analysis.
90%
With (E)-N-(pyren-1-ylmethylene)benzenamine; oxygen; palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 3h;
With [2,2]bipyridinyl; [(nickel(II))2(1,4 dicarboxybenzene)2(1,4-diaza-bicyclo[2.2.2]octane)]; 1,8-diazabicyclo[5.4.0]undec-7-ene In Hexadecane; N,N-dimethyl-formamide at 120℃; for 3h;
With tetrabutylammomium bromide; potassium carbonate; palladium dichloride; XPhos In water at 120℃; Inert atmosphere; Schlenk technique; Green chemistry;
Typical procedure for deacetonative coupling of aryl propargylic alcohols with aryl chlorides in water
General procedure: To a 25-mL Schlenk tube equipped with magnetic stir bar, aryl chloride (0.2 mmol), aryl propargylic alcohol (0.3 mmol), K2CO3 (2.0 equiv.), TBAB (1.0 equiv.), PdCl2 (2 mol%), and Xphos (4 mol%) were added in turn, then 2 mL H2O was added, and then the solution was refluxed for 24 h under N2 atmosphere. After the reaction was completed, the mixture was extracted with EtOAc or CH2Cl2. The combined organic layer was dried with anhydrous Na2SO4 and evaporated in vacuum. The crude product was purified by flash chromatography on silica gel using hexane/ethyl acetate as the eluent to afford the desired product.