chloro-di(propan-2-yl)phosphane

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

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

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Chlorodiisopropylphosphine (6.00 g, 39.3 mmol) was dissolved in THF (150 mL) and cooled to −78° C. Vinylmagnesium bromide (1 M in THF, 43.2 mL, 43.2 mmol) was added dropwise. The dry ice bath was then removed, and the reaction was allowed to warm to room temperature. After 2 h at room temperature, the reaction was quenched with saturated NH4Cl, and 30% H2O2 (75 mL) was added. The mixture was vigorously stirred at room temperature for 2 h. It was then extracted with CH2Cl2 (2×), dried (MgSO4), and evaporated. Flash chromatography (0-10% MeOH/EtOAc) afforded diisopropyl(vinyl) phosphine oxide as a colorless oil. 1H NMR (CDCl3, 600 MHz) δ 6.31 (td, J=18.6, 2.2 Hz, 1H), 6.24 (ddd, J=34.8, 12.8, 2.3 Hz, 1H), 6.03 (ddd, J=27.3, 18.7, 12.8 Hz, 1H), 2.01-1.92 (m, 2H), 1.15 (dd, J=15.0, 7.0 Hz, 6H), 1.06 (dd, J=15.9, 7.4 Hz, 6H). MS: cal'd 161 (MH+), exp 161 (MH+). The dry ice bath was then removed to warm to room temperature the reaction was quenched with saturated NH4Cl, and 30% H2O2 (75 mL) was added It was then extracted with CH2Cl2 (2×) dried (MgSO4) evaporated

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Chlorodiisopropylphosphine (6.00 g, 39.3 mmol) was dissolved in THF (150 mL) and cooled to −78° C. Vinylmagnesium bromide (1 M in THF, 43.2 mL, 43.2 mmol) was added dropwise. The dry ice bath was then removed, and the reaction was allowed to warm to room temperature. After 2 h at room temperature, the reaction was quenched with saturated NH4Cl, and 30% H2O2 (75 mL) was added. The mixture was vigorously stirred at room temperature for 2 h. It was then extracted with CH2Cl2 (2×), dried (MgSO4), and evaporated. Flash chromatography (0-10% MeOH/EtOAc) afforded diisopropyl(vinyl) phosphine oxide as a colorless oil. 1H NMR (CDCl3, 600 MHz) δ 6.31 (td, J=18.6, 2.2 Hz, 1H), 6.24 (ddd, J=34.8, 12.8, 2.3 Hz, 1H), 6.03 (ddd, J=27.3, 18.7, 12.8 Hz, 1H), 2.01-1.92 (m, 2H), 1.15 (dd, J=15.0, 7.0 Hz, 6H), 1.06 (dd, J=15.9, 7.4 Hz, 6H). MS: cal'd 161 (MH+), exp 161 (MH+). The dry ice bath was then removed to warm to room temperature the reaction was quenched with saturated NH4Cl, and 30% H2O2 (75 mL) was added It was then extracted with CH2Cl2 (2×) dried (MgSO4) evaporated

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

Procedure: To a solution of diisopropylchlorophosphine (2 mL, 12.57 mmol) in THF (25 mL) at −78° C. was added 4-tolylmagnesium bromide (12.57 mL, 12.57 mmol) dropwise. After 1 h at −78° C., the reaction mixture was let warm to RT. The solvent was removed and material was used without further purification. MS: cal'd 209 (MH+), exp 209 (MH+). The solvent was removed material was used without further purification

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N′-(2-tert-butylphenyl)-N-(2-tert-butylphenyl)-4-methylbenzamidine (NS Amidine II) (1.20 g, 3.0 mmol) was dissolved in 50 mL of diethylether and cooled to 0° C. Butyllithium (1.50 mL of 2.0 M solution in pentane, 3.0 mmol) was added dropwise, producing a light yellow solution. The solution was warmed to room temperature and stirred for 2 hours. Chlorodiisopropylphosphine (0.48 mL, 3.0 mmol) was added slowly at room temperature. A white suspension formed, which was stirred overnight at room temperature. The slurry was filtered to remove a small amount of white solid, presumably lithium chloride, and the solvent was removed in vacuo to produce 1.35 g (87%) of yellow solid. producing a light yellow solution The solution was warmed to room temperature A white suspension formed which was stirred overnight at room temperature The slurry was filtered to remove a small amount of white solid, presumably lithium chloride the solvent was removed in vacuo

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N′-(2-ethylphenyl)-N-(2-ethylphenyl)acetamidine (NS Amidine I) (0.798 g, 3.0 mmol) was dissolved in 50 mL of diethylether and cooled to 0° C. Butyllithium (1.50 mL of 2.0 M solution in pentane, 3.0 mmol) was added dropwise, producing a light yellow solution. The solution was warmed to room temperature and stirred for 2 hours. Chlorodiisopropylphosphine (0.48 mL, 3.0 mmol) was added slowly at room temperature. A white suspension formed, which was stirred overnight at room temperature. The slurry was filtered to remove a small amount of white solid, presumably lithium chloride, and the solvent was removed in vacuo to produce 1.14 g (99%) of yellow oil. producing a light yellow solution The solution was warmed to room temperature A white suspension formed which was stirred overnight at room temperature The slurry was filtered to remove a small amount of white solid, presumably lithium chloride the solvent was removed in vacuo

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N′-(2-ethylphenyl)-N-(2-ethylphenyl)acetamidine (NS Amidine I) (0.798 g, 3.0 mmol) was dissolved in 50 mL of diethylether and cooled to 0° C. Butyllithium (1.50 mL of 2.0 M solution in pentane, 3.0 mmol) was added dropwise, producing a light yellow solution. The solution was warmed to room temperature and stirred for 2 hours. Chlorodiisopropylphosphine (0.48 mL, 3.0 mmol) was added slowly at room temperature. A white suspension formed, which was stirred overnight at room temperature. The slurry was filtered to remove a small amount of white solid, presumably lithium chloride, and the solvent was removed in vacuo to produce 1.14 g (99%) of yellow oil. producing a light yellow solution The solution was warmed to room temperature A white suspension formed which was stirred overnight at room temperature The slurry was filtered to remove a small amount of white solid, presumably lithium chloride the solvent was removed in vacuo

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

Procedure: Procedure as described for NP Amidine XVII using the following amounts: 0.956 g of N1-(2-morpholinoethyl)benzamidine (Amidine XV, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mL chlorodiisopropylphosphine (5.0 mmol). After filtration to remove lithium chloride and removal of solvent, a yellow oil was isolated (1.71 g, 98%). After filtration to remove lithium chloride and removal of solvent a yellow oil was isolated (1.71 g, 98%)

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

Procedure: Procedure as described for NP Amidine I using the following amounts and modifications: 1.52 g of N1-(2-(phenylthio)phenyl)benzamidine (Amidine XIV, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mL chlorodiisopropylphosphine (5.0 mmol). After filtration to remove lithium chloride and removal of solvent, a yellow oil was isolated (2.07 g, 98%). After filtration to remove lithium chloride and removal of solvent a yellow oil was isolated (2.07 g, 98%)

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

Procedure: Procedure as described for NP Amidine I using the following amounts and modifications: 0.956 g of N1-(2-(dimethylamino)ethyl)benzamidine (Amidine XII, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mL chlorodiisopropylphosphine (5.0 mmol). After filtration to remove lithium chloride and removal of solvent, a yellow oil was isolated (1.52 g, 99%). After filtration to remove lithium chloride and removal of solvent a yellow oil was isolated (1.52 g, 99%)

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

Procedure: Procedure as described for NP Amidine I using the following amounts and modifications: 0.956 g of N1-(2-(dimethylamino)ethyl)benzamidine (Amidine XII, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mL chlorodiisopropylphosphine (5.0 mmol). After filtration to remove lithium chloride and removal of solvent, a yellow oil was isolated (1.52 g, 99%). After filtration to remove lithium chloride and removal of solvent a yellow oil was isolated (1.52 g, 99%)