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With potassium acetate In N,N-dimethyl acetamide at 130℃; for 3 h; Schlenk technique; Inert atmosphere
General procedure: MCM-41-3N-Pd(0) (21mg, 0.01mmol), KOAc (1.5mmol) and aryl iodide 1 (1.0mmol) (if solid) were placed in an oven-dried 20mL Schlenk tube, the reaction vessel was evacuated and filled with argon for three times. Then aryl iodide 1 (1.0mmol) (if liquid), diphenylphosphine (1.2mmol) and DMAc (1mL) were added with a syringe under a counter flow of argon. The reaction mixture was stirred at 130°C for 3h. After completion of the reaction, the mixture was cooled to room temperature and diluted with CH2Cl2 (20mL) and filtered. The MCM-41-3N-Pd(0) catalyst was washed with distilled water (2×5mL) and ethanol (2×5mL), and reused in the next run. The filtrate was concentrated in vacuo and the residue was purified by flash column chromatography on silica gel to provide the product 2.
With palladium diacetate; caesium carbonate In toluene at 80℃; for 12 h; Sealed tube; Inert atmosphere
General procedure: In a sealed vial, under nitrogen, p-methylbenzoyldiphenylphosphine (61 Cs2CO3 mg, 0.20 mmol, 1.0 equiv), Pd(OAc)2 (1.4 mg, 0.006 mmol), aryl iodides (0.21mmol, 1.05 equiv), (72 mg, 0.22 mmol, 1.1 equiv) and toluene (0.5 mL) were mixed and stirred at 80 oC for 12 h. When reaction completed, the reaction mixture was directly purified by flash column chromatography on silica gel to give pure product.
With potassium acetate; In N,N-dimethyl acetamide; at 130℃; for 3h;Schlenk technique; Inert atmosphere;
General procedure: MCM-41-3N-Pd(0) (21mg, 0.01mmol), KOAc (1.5mmol) and aryl iodide 1 (1.0mmol) (if solid) were placed in an oven-dried 20mL Schlenk tube, the reaction vessel was evacuated and filled with argon for three times. Then aryl iodide 1 (1.0mmol) (if liquid), diphenylphosphine (1.2mmol) and DMAc (1mL) were added with a syringe under a counter flow of argon. The reaction mixture was stirred at 130°C for 3h. After completion of the reaction, the mixture was cooled to room temperature and diluted with CH2Cl2 (20mL) and filtered. The MCM-41-3N-Pd(0) catalyst was washed with distilled water (2×5mL) and ethanol (2×5mL), and reused in the next run. The filtrate was concentrated in vacuo and the residue was purified by flash column chromatography on silica gel to provide the product 2.
(E)-ethene-1,2-diylbis((4’-biphenyl)diphenylphosphonium)ditriflate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
at 120℃; for 24h;Inert atmosphere; Schlenk technique;
General procedure: A. TfOCH2CF2H(0.514 g, 2.4 mmol) and triphenylphosphine (0.525 g, 2 mmol) were placed in aclosed Schlenk flask under a N2 atmosphere. The mixture was stirredat 120 oC for 24 h and cooled to room temperature. The resultingsolid was washed by diethyl ether, recrystallized from CH2Cl2/hexane,and dried in vacuum to give 0.66 g of (E)-ethene-1,2-diylbis(triphenylphosphonium)ditriflate (3a) as a white solid (0.78 mmol, 78percent).2
With palladium diacetate; caesium carbonate; In toluene; at 80℃; for 12h;Sealed tube; Inert atmosphere;
General procedure: In a sealed vial, under nitrogen, p-methylbenzoyldiphenylphosphine (61 Cs2CO3 mg, 0.20 mmol, 1.0 equiv), Pd(OAc)2 (1.4 mg, 0.006 mmol), aryl iodides (0.21mmol, 1.05 equiv), (72 mg, 0.22 mmol, 1.1 equiv) and toluene (0.5 mL) were mixed and stirred at 80 oC for 12 h. When reaction completed, the reaction mixture was directly purified by flash column chromatography on silica gel to give pure product.
bis[2-(diphenylphosphino)biphenyl] copper(I) iodide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84.2%
In dichloromethane; at 20℃; for 3h;
A suspension of copper(I) iodide (0.042 g, 0.22 mmol) and dpbp (0.149 g, 0.44 mmol) in 15 mL ofCH2Cl2 was stirred for 3 h at room temperature to form a white precipitate. The precipitate was filteredoff and purified by recrystallization from CH2Cl2/aectonitrile to give colorless crystals (Yield: 0.160 g,84.2percent). 1H NMR (400 M, CDCl3) delta: 7.44?7.26 (m, 26H, m,p-Ph + ?PC6H4?), 7.09?6.99 (m, 12H, o-Ph). 13CNMR (100 M, CDCl3) delta: 147.87, 147.67, 140.24, 140.16, 134.31, 134.17, 133.45, 132.17, 131.81, 131.07,130.71, 130.14, 129.90, 128.93, 128.69, 127.93, 127.26 (Ar?C). 31P NMR (240 M, CDCl3) delta ?10.16 (s). Anal.Calcd for C48H38CuIP2: C, 66.48; H, 4.42. Found: C, 66.50; H, 4.40. MS (MALDI-TOF): m/z Calcd for [M?I]+,739.1745, found 739.1874.
2',6'-diphenylbiphenyl-2-yldiphenylphosphine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; lithium tert-butoxide; In 1,4-dioxane; at 140℃; for 36h;Schlenk technique; Inert atmosphere;
In a 25 mL Schlenk tube,Was added 67.7 mg (0.2 mmol) of 2-dicyclohexylphosphino biphenyl (PhJohnPhos)(1,5-cyclooctadiene) chlorineRhodium (I) dimer 2.5 mg (2.5percent of the molar number of raw materials)Lithium tert-butoxide48 mg (0.6 mmol) was added, and argon was replaced three times with 1 mL of 1,4-dioxane and 75.4 mg (0.48 mmol) of bromobenzene under argon.After stirring at 140 ° C for 36 hours, the mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The solvent was separated on a 200-300 mesh silica gel column. The petroleum ether: ethyl acetate = 100: 1The product was eluted and dried in vacuo to give 84.6 mg of product as a white solid in 86percent yield.
With chloro(1,5-cyclooctadiene)rhodium(I) dimer; lithium tert-butoxide; In 1,4-dioxane; at 90℃; for 48h;Schlenk technique; Inert atmosphere;
25 mL of Schlenk tube, 67.7 mg (0.2 mmol) of 2-diphenylphosphine biphenyl (PhJohnPhos)(1,5-cyclooctadiene) chlorineRhodium (I) dimer 1.0 mg (1percent of the moles of the starting material)Lithium tert-butoxide48 mg (0.6 mmol) was added, and argon was replaced three times, and 1 mL of 1,4-dioxane and 31.4 mg (0.2 mmol) of bromobenzene were added under argon. 90 ° C for 48 hours and cooled to room The solvent was distilled off under reduced pressure, separated by 200-300 mesh silica gel column, petroleum ether: ethyl acetate = 100: 1, vacuum After drying the product was 69.3 mg of a white solid in 84percent yield.
A solution of CuI (0.019 g, 0.1 mmol) in CH3CN(5 mL) wasadded to a stirred solution of 1,10-phenanthroline (0.018 g,0.1 mmol) and 2-(Dpp)bp (0.034 g, 0.1 mmol) in EtOAc(5 mL). The mixture was stirred for 5 min and then the precipitatewas filtered off. The resultant clear solution was setaside for evaporation in air. Orange block crystals of complex1 were obtained after 1 day and red crystals of complex2 were obtained the next day. These two different productswere separated manually under a microscope. Yield: 20.0 mg(28.2percent, based on Cu) for 1 and 24.4 mg (27.1percent, based onCu) for 2. Anal. Calc. for 1 C36H27N2P1Cu1I1:C, 60.98; H,3.81; N, 3.95. Found (percent): C, 61.04; H, 3.81; N, 3.88. IR(KBr pellet, cm?1): 3446sh, 3004s, 1789m, 1639m, 1550s,1448m, 1209w, 1120m, 716m; for 2 C36H27N2P1Cu2I2:C,48.07; H, 3.03; N, 3.12. Found (percent): C, 48.14; H, 3.04; N,3.04. IR (KBr pellet, cm?1): 3522sh, 3004s, 1639w, 1461m,1221s, 930s, 868s.
A solution of CuI (0.019 g, 0.1 mmol) in CH3CN(5 mL) wasadded to a stirred solution of 2,2?-Bipy (0.016 g, 0.1 mmol)and 2-(Dpp)bp (0.034 g, 0.1 mmol) in CH3CN(5 mL). Themixture was stirred for 10 min, with no visible precipitation.After filtration, the clear filtrate was set aside for evaporationin air. Orange block crystals of complex 4 were obtainedafter several hours. Yield: 43.4 mg (63.4percent, based on Cu).Anal. Calc. for 4 C34H27N2P1Cu1I1:C, 59.63; H, 3.94; N,4.09. Found (percent): C, 59.64; H, 3.92; N, 3.98. IR (KBr pellet,cm?1): 3430sh, 3054vw, 1610m, 1431s, 1146w, 1103w,770, 699.
A solution of CuI (0.019 g, 0.1 mmol) in CH3CN(5 mL)was added to a stirred solution of 2-PBI (0.020 g, 0.1 mmol)and 2-(Dpp)bp (0.034 g, 0.1 mmol) in CH2Cl2(5 mL). Themixture was stirred for 5 min, with no visible precipitation.After filtration, the filtrate was set aside for evaporation inair. Yellow block crystals of complex 3 were obtained after3 days. Yield: 35.1 mg (48.5percent, based on Cu). Anal. Calc. for3 C36H28N3P1Cu1I1:C, 59.73; H, 3.87; N, 5.81. Found (percent):C, 59.72 H, 3.84; N, 5.78. IR (KBr pellet, cm?1): 3443sh,3077vs, 3054s, 1610w, 1491m, 1443vs, 1326m, 1114w,805m, 746vs, 711vs, 522m.
2''-methoxy-([1,1':2',1''-terphenyl]-2-yl)diphenylphosphane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
With [RhCl2(p-cymene)]2; N-acetyl-beta-alanine; cesium acetate; In toluene; at 120℃; for 18h;
1.453 g of 2-diphenylphosphine-biphenyl, 1.404 g of 2-iodoanisole, 122.5 mg of cymene dichloride dimer, and 78.7 mg of N-Ac-beta-alanine were added to the reactor. 1.536 g of cesium acetate and 2 mL of toluene, the reaction temperature was controlled at 120 ° C for 18 hours, then cooled to room temperature, filtered through celite and distilled under reduced pressure to give 1.76 g of product.95percent.
3-(2'-(diphenylphosphino)-[1,1'-biphenyl]-2-yl)propionic acid tert-butyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
With BOC-glycine; [RhCl2(p-cymene)]2; P(p-CH3OC6H4)3; potassium acetate; In hexane; at 120℃; for 24h;Inert atmosphere;
101.4 mg (0.3 mmol) was added to the reaction kettle.2-diphenylphosphine-biphenyl (compound I-2),141 muL of tert-butyl acrylate (Compound II-2), 9.3 mg of cymene dichloride dimer, 15.8 mg of N-Boc-glycine, 5.3 mg of tris(4-methoxyphenyl)phosphine,58.8 mg of potassium acetate and 1.5 mL of n-hexane,After stirring and mixing uniformly, argon gas is introduced into the reaction system to control the reaction in an argon atmosphere.The temperature was reacted at 120 C for 24 h and then cooled to room temperature.Separation of diatomaceous earth by vacuum filtration and column chromatography101 mg of the desired product in a yield of 72%.
3-(2'-(diphenylphosphino)-[1,1'-biphenyl]-2-yl)propanoic acid ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With BOC-glycine; [RhCl2(p-cymene)]2; P(p-CH3OC6H4)3; potassium acetate; In hexane; at 120℃; for 24h;Inert atmosphere;
101.4 mg (0.3 mmol) of 2-diphenylphosphine-biphenyl (Compound I-1) and 82.5 muL of ethyl acrylate (Compound II-1, 0.76 mmol) were added to the reaction vessel.9.3 mg p-cymene dichloride dimer, 15.8 mg N-Boc-glycine,5.3 mg of tris(4-methoxyphenyl)phosphine, 58.8 mg of potassium acetate and 1.5 mL of n-hexane,After stirring and mixing uniformly, argon gas is introduced into the reaction system to control the reaction in an argon atmosphere.The temperature was reacted at 120 C for 24 h, then cooled to room temperature, and filtered through celite.After distillation under reduced pressure, 93.8 mg of the target product was obtained by column chromatography.The yield was 71%.
[Fe2(CO)5{Ph2P(2‑C6H4Ph)}{μ‑SC6H3(CH3)S}][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With trimethylamine-N-oxide dihydrate; In dichloromethane; acetonitrile; at 20℃; for 1h;
General procedure: To a solution of [Fe2(CO)6{mu-SC6H3(CH3)S}] (0.043 g,0.1 mmol) and ethyl diphenylphosphinite (0.023 g,0.1 mmol) in CH2Cl2(5 mL) was added a solution of Me3NO·2H2O (0.011 g, 0.1 mmol) in MeCN (5 mL). The mixture was stirred at room temperature for 1 h and then the solvent was reduced on a rotary evaporator. The residue was subjected to TLC using CH2Cl2/petroleum ether = 1:4(v/v) as eluent.