- Production Method of (R)-2,2'-Binaphthoyl-(S,S)-di-(1-phenylethyl)aminoylphosphine
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(R)-2,2'-Binaphthoyl-(S,S)-di-(1-phenylethyl)aminoylphosphine could be produced through the following synthetic routes.
A. (R)-(-)-(-2,2'-dioxy)chlorophosphine [1].2 A 250-mL, single-necked round-bottomed flask, equipped with a magnetic stirring bar, a reflux condenser, a three-way flow-controlled stopcock is flame-dried and purged with nitrogen. All joints are greased. The nitrogen outlet is connected to a gas scrubber trap. The flask is charged with (R)-(+)-1,1'-bi(2-naphthol) (7.0 g, 24.5 mmol) and phosphorus trichloride (20.5 mL, 32.3 g, 235 mmol, 9.6 equiv) followed by 1-methyl-2-pyrrolidinone (20 μL, 0.2 mmol, 0.008 equiv). The flask is placed in an oil bath preheated to 92 °C. The solid dissolves within 5 min. The flask is swirled to dissolve the solid on the side. During this period, HCl evolves rapidly and the solution becomes yellow. The solution is kept at reflux for 10 min, then the oil bath is removed and the reaction mixture is allowed to cool to ambient temperature. The remaining phosphorus trichloride and HCl are removed under reduced pressure (7 mmHg) for 2 h, leaving a foamy wax. After venting the flask with nitrogen, diethyl ether (30 mL) is added to dissolve the solid. The solvent and traces of phosphorus trichloride are removed under reduced pressure (7 mm Hg) for 2 h, leaving a pale-yellow solid. The flask is connected to high vacuum (0.05 mm Hg) for 12 h to afford 9.08 g (106 %) of the desired product as off-white powder containing traces of diethyl ether.B. (R)-2,2'-Binaphthoyl-(S,S)-di-(1-phenylethyl)aminoylphosphine [3].3 A 250-mL, three-necked flask equipped with a rubber septum, nitrogen inlet, and a temperature probe is flame-dried and purged with nitrogen. The flask is charged with anhydrous THF (35 mL) and (-)-bis-[(S)-1-phenylethyl]amine (2, 1.69 mL, 7.39 mmol). The solution is cooled to -78 °C in a dry ice-acetone bath. (4.62 mL, 7.39 mmol, 1.6 M solution in hexanes, 1.0 equiv) is added dropwise over a 15 min period maintaining the internal temperature below -68 °C until the addition is complete, resulting in a pale-pink solution. The contents of the flask are warmed to -30 °C in about 30 min and immediately cooled to -78 °C for an additional 1 h, which results in the solution becoming dark pink. A solution of (R)-(-)-1,1'-binaphthyl-2,2'-dioxychlorophosphine (1, 2.85 g, 8.13 mmol, 1.1 equiv) in dry THF (10 mL) is then introduced dropwise via syringe maintaining the solution temperature below -68 °C. The solution is maintained at -78 °C for an additional 2 h before it is warmed to ambient temperature and allowed to stir for 12 h. The solvent is removed by rotary evaporation (23 °C, 20 mmHg) to afford a pale-yellow oil mixed with a white solid. The residue is dissolved in 5 mL of dichloromethane, then is loaded onto a silica gel column (150 g, 50 cm × 5 cm) and is eluted with 2 L of pentane/dichloromethane, 4:1. Removal of the solvent from the eluate by rotary evaporation (23 °C, 20 mmHg) followed high vacuum (~ 0.05 mm Hg) affords 3.43 g (86%) of (R)-2,2'-binaphthoyl-(S,S)-di(1-phenylethyl)aminoyl-phosphine (3) as a white foam, mp 106–110 °C. This product can be crushed into a powder and weighed as needed.
Notice: Decomposition of excess PCl3 (step A) should be carried out carefully in a fume-hood because hydrogen chloride is evolved in the highly exothermic hydrolysis reaction.
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