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With sodium hydroxide; trichlorosilane; 2,3-Dimethylaniline In toluene
12 Synthesis of (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl
Example 12 Synthesis of (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl Trichlorosilane (0.95 ml, 9.4 mmol) was added to a mixture of (R)-2-diphenylphosphino-2'-diphenylphosphinyl-1,1'-binaphthyl (1.5 g, 2.35 mmol), dimethylaniline (4.8 ml, 4.4 mmol) and toluene (11 ml). The resulting reaction mixture was stirred for 1 hour at 90° C. and thereafter heated at reflux for 16 hours. The reaction mixture was cooled in an ice/water bath, and 3N NaOH solution (20 ml) was added to the reaction mixture. The aqueous layer was extracted with toluene and the organic layer was washed with water (10 ml), 1N hydrochloric acid (20 ml) and water (10 ml) in that order, followed by concentrating the organic solution. Then, the organic solution was purified by silica gel column chromatography (hexane:ethyl acetate=1:0 to 1:1 by volume) to obtain 1.34 g (yield: 92%) of the above captioned compound as a white solid. mp: 241 to 242° C. [α]D24: -228° (c 0.679, benzene) 31 P-NMR(CDCl3)δ: -12.8(s) CI-Mass spectrum m/z: 622(M+)
92%
With hydrogenchloride; sodium hydroxide; trichlorosilane; 2,3-Dimethylaniline In water; toluene
2.2 (2)
(2) Synthesis of (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl 0.95 ml (9.4 mmol) of trichlorosilane was added to a mixture comprising 1.5 g (2.35 mmol) of (R)-2-diphenylphosphinyl-2'-diphenylphosphino-1,1'-binaphthyl, 4.8 ml (4.4 mmol) of dimethylaniline and 30 ml of toluene. The resultant mixture was then stirred at 90° C. for 1 hour and for 16 hours while refluxing. The reaction mixture thus obtained was cooled in an ice water bath, and 20 ml of a 3 N NaOH solution was added thereto. The resultant aqueous layer was extracted with toluene. The thus obtained organic layer was then washed with 10 ml of water, with 20 ml of a 1 N hydrochloric acid solution, and with 10 ml of water. After concentration, the resultant solution was purified by silica gel chromatography (hexane:ethyl acetate=1:0 to 1:1) to obtain 1.34 g (yield 92%) of the objective compound as a white solid. The physico-chemical properties of the product were measured as follows. mp 241° to 242° C. [α]D24 -228° (c 0.68, benzene) 31 P NMR (CDCl3) δ-12.8(s) CI-Mass spectrum m/z 622 (M+)
43 %
With phenylsilane; 1-bromo-4-methyl-1-phenyl-2,3-dihydro-1H-phosphol-1-ium bromide; Diethyl 2-bromomalonate In 1,2-dichloro-ethane at 20℃; Inert atmosphere; Schlenk technique;
In methanol; dichloromethane at 50℃; for 0.333333h;
8
A Schlenk flask under nitrogen is charged with 101.7 mg of (S)-BINAP (0.1633 mmol) and 50 mg of [(p~cymene)RuCl2]2 (0.0816 mmol) and charged with 5ml of dry degassed EPO dichloromethane and 0.625ml of dry degassed methanol. The solution is heated to 50°C for 20 minutes before removing the solvent in vacuo to give a yellow crystalline solid. 18.65mg of (R1R)-DACH (0.1633 mmol) are added with 5ml of dry degassed tetrahydrofuran and heated at 60°C for 4 hours. The reaction is cooled to room temperature. 31P NMR reveals essentially a single species and no starting materials. 31P NMR reveals >95% product and conversion. The solvent is removed in vacuo to give a pale yellow amorphous solid.31P NMR (162 MHz, CDCl3) 546.42 ppm, singlet.
dichloro(1,5-cyclooctadiene)ruthenium(II)[ No CAS ]
[ 261948-85-0 ]
Yield
Reaction Conditions
Operation in experiment
With sodium acetate; triethylamine In toluene; <i>tert</i>-butyl alcohol react. of (RuCl2(cod))2 with (R)-BINAP and N(C2H5)3 in toluene, then addn. of NaO2CCH3;;
bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II)[ No CAS ]
[ 132071-87-5 ]
Yield
Reaction Conditions
Operation in experiment
In methanol; acetone Ru complex and (S)-2,2'- bis(diphenylphosphino)-1,1'-binaphthyl placed in glass tube; evacuated; filled with Ar; soln. of HCl in MeOH added to anhyd. acetone; degassed; injected to mixt. of ligand and Ru complex; mixt. stirred for 0.5 h; solvent evapd. (vac.);
[bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II)[ No CAS ]
[ 98327-87-8 ]
[ 64-19-7 ]
[ 261948-85-0 ]
Yield
Reaction Conditions
Operation in experiment
91%
In toluene N2, a soln. of Ru compd. and P compd. refluxed for 4 h, solvent evapd. (vac.), ether soln. of acetic acid added at room temp., stirred for 10-14h; elem. anal.;
In N,N-dimethyl-formamide the binaphthyl is added to the Ru-complex under N2, DMF is added and the suspn. is heated to 100°C with stirring for 10 min; solvent is removed and residue is dissolved in THF;
With sodium carbonate In dimethyl sulfoxide K2PtCl4, 2-vanillin amd Na2CO3 are mixed with DMSO under N2, heated to 140°C with stirring, for 30 min, cooled down to 100°C, thephosphine is added, further ooling to 60°C; the solvent is evapd., the residue is extd., filtd., the fitrate is treated mith activated carbon, after 15 min filtd, concd., addn. of EtOH, the ppt. is filtd., washed, dried, elem. anal.;
With sodium carbonate In dimethyl sulfoxide Ar atmosphere, stirring of K2PtCl4, Na2CO3 and aldehyde (140°C, 40 min), addn. of phosphine after slow cooling to 100°C, cooling to 60°C; removement of solvent (vacuum), extn. (CH2Cl2), filtration, redn. of volume, addn. (EtOH), pptn., washing (EtOH), drying (50°C, 3 h, vacuum); elem. anal.;
With sodium carbonate In dimethyl sulfoxide Ar atmosphere, stirring of K2PtCl4, Na2CO3 and aldehyde (140°C, 40 min), addn. of phosphine after slow cooling to 100°C, cooling to 60°C; removement of solvent (vacuum), extn. (CH2Cl2), filtration, redn. of volume, addn. (EtOH), pptn., washing (EtOH), drying (50°C, 3 h, vacuum); elem. anal.;
Stage #1: dichloro(benzene)ruthenium(II) dimer; (S)-(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine) In N,N-dimethyl-formamide at 100℃; for 1h; Inert atmosphere;
Stage #2: (S)-α-methyl-1H-benzimidazole-2-methanamine In dichloromethane at 20℃; for 5h; Inert atmosphere;
5
The complex [RuCl2(benzene)]2 (6.6 mg, 0.013 mmol) and (,S)-BINAP (16.4 mg, 0.026 mmol) were suspended in 3 ml of degassed DMF. After stirring for 1 hour at 100 0C, the solvent was removed under high vacuum at 50 0C for 2 hours. After (-S)-Me-bimaH (4.3 mg, 0.026 mmol) and 3 ml of degassed CH2Cl2 were added following 5 -hours stirring at room temperature, the volume of the solution was redued to about 0.5 ml and the complex was precipitated by adding 5 ml of hexane. The solid was obtained by filtration following with dryness under vacuum.Yield 19 mg (71%). 31P(1H) NMR (121 MHz, CDCl3, 20 0C) δ (ppm) 49.58 (d, J= 38.7 Hz), 47.32 (d, J= 38.7 Hz); MS(MALDI) m/z: 884 [M-71]+.
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