chloro(dicyclohexyl)phosphane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1 (535 mg, 2.03 mmol) in THF (20 mL) was cooled to −78° C. under argon, then n-BuLi (1.6 M in hexane, 1.35 mL, 2.16 mmol) was added dropwise. After 2.5 h at −78° C., a solution of chlorodicyclohexylphosphine (570 mg, 2.45 mmol) in THF (3 mL) was added over 10 min. The reaction mixture was then allowed to warm to room temperature overnight, then quenched with saturated aqueous NaHCO3 and concentrated in vacuo. The resulting aqueous suspension was extracted with ether (2×50 mL), and the combined ethereal layers were dried (Na2SO4), filtered and concentrated in vacuo. The resulting crude solid was recrystallized from ethanol to afford 420 mg (54%) of a white solid. quenched with saturated aqueous NaHCO3 concentrated in vacuo The resulting aqueous suspension was extracted with ether (2×50 mL) the combined ethereal layers were dried (Na2SO4) filtered concentrated in vacuo The resulting crude solid was recrystallized from ethanol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: n-Butyllithium (manufactured by Kanto Chemical Co., Inc., 1.65 M hexane solution, 5.1 ml, 8.4 mmol) was added to a tetrahydrofuran (THF) solution (20 ml) of benzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 0.66 g, 4.2 mmol) at 0° C. under argon atmosphere and the mixture was stirred for 2.5 hours at room temperature. After cooling the reaction container to −78° C., chlorodicyclohexylphosphine (manufactured by Sigma-Aldrich, 0.89 mg, 3.8 mmol) was added thereto at −78° C. and stirred for 24 hours at room temperature. After ceasing the reaction with trifluoroacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 0.50 M THF solution, 8.4 ml, 4.2 mmol), the precipitate formed was collected by filtration and dried under reduced pressure to obtain 2-(dicyclohexylphosphino)benzenesulfonic acid (compound 1a). The yield was 0.66 g (85%). After cooling the reaction container to −78° C. at −78° C. and stirred for 24 hours at room temperature the precipitate formed was collected by filtration dried under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1,3-dimethoxybenzene (2 ml, 15.30 mmol) in anhydrous THF (35 ml) at 0° C., nBuLi (6.2 ml, 15.50 mmol) is added to the dropping funnel for 5 min. The reaction medium is stirred at room temperature for 3.5 h, then 2-bromochlorobenzene (1.6 ml, 13.70 mmol) is added by syringe, dropwise, at 0° C., for 30 min. After 15 min of stirring, the reaction medium is cooled to −78° C. and nBuLi (6.20 ml, 15.50 mmol) is added to the dropping funnel dropwise for 5 min. After 30 min, chlorodicyclohexylphosphine (3.03 ml, 13.70 mmol) is added. The reaction medium is maintained at −78° C. for 1 h, under rapid stirring (mechanical stirring). After returning to room temperature, the precipitate obtained is filtered on a fritted disc containing silica topped with a layer of cellulose acetate, with 600 ml ethyl acetate. The solvents are evaporated with a rotary evaporator, and the orange oil obtained is recrystallized in acetone to obtain S-Phos ligand in the form of white crystals with a yield of 36% (1.22 g, 2.97 mmol). dropwise, at 0° C., for 30 min After 15 min of stirring the reaction medium is cooled to −78° C. After 30 min The reaction medium is maintained at −78° C. for 1 h under rapid stirring (mechanical stirring) After returning to room temperature the precipitate obtained is filtered on a fritted disc containing silica The solvents are evaporated with a rotary evaporator the orange oil obtained is recrystallized in acetone

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a dry round bottom flask under argon, an ice-cold solution of dimethylaminoferrocene 11 (229 mg, 1.00 mmol) in THF (10 mL) was treated with BF3.OEt2 (0.13 mL, 1.05 mmol). After 15 min, the yellow solution was cooled to −40° C. and n-BuLi (0.46 mL of 2.40 M solution in hexanes, 1.10 mmol) was added by syringe to give an orange-red solution that was stirred for 1 h before ClPCy2 (0.24 mL, 1.10 mmol) was added and the mixture was allowed to warm to room temperature. The reaction mixture was diluted with Et2O (10 mL) and worked up with saturated aqueous NaHCO3 solution (10 mL). The organic layer was washed with H2O (1×10 mL), brine (1×10 mL), dried over anhydrous Na2SO4 and concentrated to dryness. The residue was redissolved in pentane and chromatographed on silica gel (25 mL), eluting with 95:5 pentane/Et2O to give 397 mg (77%) of the desired aminophosphine 12j as a moderately air-sensitive viscous orange oil. Rf (SiO2, 9:1 hex/EtOAc) 0.50; IR (CHCl3): vmax 2920, 2848, 1489, 1446 cm−1, 31P NMR (121 MHz, acetone-d6): δ −12.3; 1H NMR (300 MHz, acetone-d6): δ 4.22 (s, 5H), 4.15 (t, 1H, J=1.1 Hz), 4.04 (t, 1H, J=2.3 Hz), 3.92 (t, 1H, J=1.7 Hz), 2.75 (s, 6H), 2.49-2.41 (m, 1H), 2.00-1.93 (m, 1H), 1.92-1.81 (m, 3H), 1.77-1.67 (m, 2H), 1.67-1.61 (m, 1H), 1.61-1.52 (m, 3H), 1.50-1.20 (m, 7H), 1.20-1.06 (m, 2H), 1.06-0.97 (m, 1H), 0.90-0.79 (m, 1H); 13C NMR (75.5 MHz, acetone-d6) δ 118.0 (d, J13C-31P=14.0 Hz), 67.5, 66.6 (d, J13C31P=3.4 Hz), 63.3 (d, J13C-31P=25.3 Hz), 63.2, 61.3 (d, J13C-31P=1.5 Hz), 43.9 (d, J13C-31P=13.2 Hz), 35.0 (d, J13C-31P=15.9 Hz), 33.2 (d, J13C-31P=13.2 Hz), 32.2 (d, J13C-31P=20.6 Hz), 30.2 (d, J13C-31P=15.9 Hz), 29.5 (d, J13C-31P=10.8 Hz), 29.0, 27.3 (d, J13C-31P=11.8 Hz), 27.2 (d, J13C-31P=6.5 Hz), 27.0 (d, J13C-31P=12.8 Hz), 26.8 (d, J13C-31P=8.3 Hz), 26.3 (d, J13C-31P=15.5 Hz). EIMS (m/z (%)): 425 (M+, 87), 130 (62), 55 (100), 41 (94); HRMS (EI; m/z): calcd for C24H36NP56Fe 425.1936. Found 425.1934. to give an orange-red solution that was added to warm to room temperature The organic layer was washed with H2O (1×10 mL), brine (1×10 mL) dried over anhydrous Na2SO4 concentrated to dryness The residue was redissolved in pentane chromatographed on silica gel (25 mL) eluting with 95:5 pentane/Et2O

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.6 ml (15 mmol.) of TMEDA are added to 1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours, reflux (75° C.), the colour has deepened from yellow to orange. Without cooling, a solution of 2.2 ml (10 mmol.) of chlorodicyclohexylphosphane in 20 ml of hexane is added dropwise. Refluxing is carried out for a further one hour, the colour of the mixture lightening again and a white solid precipitating. After cooling, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2SO4 and concentrated in vacuo (45° C.). The yellow residue is boiled for 30 minutes in 30 ml of MeOH. After cooling to RT, the resulting product is filtered off (660 mg, 17%). Without cooling Refluxing is carried out for a further one hour the colour of the mixture lightening again and a white solid precipitating After cooling 30 ml of water are added to the mixture The aqueous phase is extracted 3 times The combined organic phases are washed with 10 ml of water dried over Na2SO4 concentrated in vacuo (45° C.) The yellow residue is boiled for 30 minutes in 30 ml of MeOH After cooling to RT the resulting product is filtered off (660 mg, 17%)

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.6 ml (15 mmol.) of TMEDA are added to 1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours, reflux (75° C.), the colour has deepened from yellow to orange. Without cooling, a solution of 2.2 ml (10 mmol.) of chlorodicyclohexylphosphane in 20 ml of hexane is added dropwise. Refluxing is carried out for a further one hour, the colour of the mixture lightening again and a white solid precipitating. After cooling, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2SO4 and concentrated in vacuo (45° C.). The yellow residue is boiled for 30 minutes in 30 ml of MeOH. After cooling to RT, the resulting product is filtered off (660 mg, 17%). Without cooling Refluxing is carried out for a further one hour the colour of the mixture lightening again and a white solid precipitating After cooling 30 ml of water are added to the mixture The aqueous phase is extracted 3 times The combined organic phases are washed with 10 ml of water dried over Na2SO4 concentrated in vacuo (45° C.) The yellow residue is boiled for 30 minutes in 30 ml of MeOH After cooling to RT the resulting product is filtered off (660 mg, 17%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.6 ml of TMEDA (15 mmol.) are added to a suspension of 1.86 g (10 mmol.) of N-mesitylimidazole in 30 ml of hexane. 6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 2.2 ml (10 mmol.) of dicyclohexylchlorophosphane are mixed with 20 ml of hexane and heated to 60° C. (solution 2). The boiling solution 1 is then slowly transferred into solution 2, which is at 60° C., by means of a cannula. The mixture is then boiled for a further 1 hour at reflux, the solution is cooled, and 20 ml of degassed water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacua; 30 ml of pentane are added thereto, and the mixture is boiled for 1 hour at reflux. The product precipitates in crystalline form at −30° C. and is filtered off while cold. Yield: 2.48 g (65%) The mixture is then heated for 2.5 hours is at 60° C., by means of a cannula at reflux the solution is cooled The organic phase is filtered off over magnesium sulfate The solution is concentrated in vacua 30 ml of pentane are added the mixture is boiled for 1 hour at reflux The product precipitates in crystalline form at −30° C. is filtered off while cold

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 19 g (0.1 mol) dicyclohexylphosphine in 50 ml toluene was dropped into a suspension of 21 g (0.1 mol) PCl5 in 100 ml toluene. The reaction temperature was maintained at less than 30° C. After all had been dropped in, the whole was boiled for 1 hour under reflux. A slight precipitate was removed by means of a reverse frit and the reaction mixture was freed from all low boilers at 60° C. under 0.1 mbar. Yield: 23.3 g; 31P-NMR: δ P=126 ppm, (c-C6H11)2PCl, 96 mol %; δ P=54 ppm, (c-C6H11)2P(O)Cl, 3.7 mol %. The reaction temperature was maintained at less than 30° C After all had been dropped in, the whole under reflux A slight precipitate was removed by means of a reverse frit was freed from all low boilers at 60° C. under 0.1 mbar

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1 (535 mg, 2.03 mmol) in THF (20 mL) was cooled to −78° C. under argon, then n-BuLi (1.6 M in hexane, 1.35 mL, 2.16 mmol) was added dropwise. After 2.5 h at −78° C., a solution of chlorodicyclohexylphosphine (570 mg, 2.45 mmol) in THF (3 mL) was added over 10 min. The reaction mixture was then allowed to warm to room temperature overnight, then quenched with saturated aqueous NaHCO3 and concentrated in vacuo. The resulting aqueous suspension was extracted with ether (2×50 mL), and the combined ethereal layers were dried (Na2SO4), filtered and concentrated in vacuo. The resulting crude solid was recrystallized from ethanol to afford 420 mg (54%) of a white solid. quenched with saturated aqueous NaHCO3 concentrated in vacuo The resulting aqueous suspension was extracted with ether (2×50 mL) the combined ethereal layers were dried (Na2SO4) filtered concentrated in vacuo The resulting crude solid was recrystallized from ethanol