Ruthenium-diamine complex and method for producing optically active compound
a technology of ruthenium diamine and complex, which is applied in the field of ruthenium diamine complex, can solve the problems of insufficient catalytic activity or excess enantiomeric excess, and achieve excellent stereoselectivity, high enantiomeric excess, and high catalytic activity.
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example 1
[0062]Production of 4-(4-methylcyclohexa-1,4-dienyl)butan-1-ol and 4-(5-methylcyclohexa-1,4-dienyl)butan-1-ol
[0063]In 45 mL of THF, 1,2-bis(diphenylphosphino)ethane (0.77 g, 1.93 mmol), cobalt bromide 0.41 (0.41 g, 1.87 mmol), zinc iodide (1.19 g, 3.73 mmol), and zinc (0.24 g, 3.67 mmol) were dissolved, followed by stirring at 70° C. for 15 minutes. After cooling to room temperature, isoprene (7.55 g, 110.83 mmol) was added. Then, 5-hexyn-1-ol (8.94 g, 91.09 mmol) was slowly added dropwise with cooling in a water bath. After stirring at 35° C. for 1 hour, the solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate=3 / 1). Thus, 13.34 g of the title compounds, alcohols, were obtained as a colorless oily substance. Yield: 88.1% (isomer ratio: 1,4 type / 1,5 type=77 / 23). Note that the following NMR spectrum data are those of the isomer mixture.
[0064]1H-NMR (CDCl3, 300 MHz): δ 5.61-5.57 (m, 2H′), 5.43-5.4...
example 2
[0066]Production of 4-(4-methylcyclohexa-1,4-dienyl)butyl 4-methylbenzenesulfonate and 4-(5-methylcyclohexa-1,4-dienyl)butyl 4-methylbenzenesulfonate
[0067]The alcohols (12.19 g, 73.32 mmol, isomer ratio: 1,4 type / 1,5 type=77 / 23) obtained in Example 1, triethylamine (8.90 g, 87.98 mmol), and 1-methylimidazole (7.22 g, 87.98 mmol) were dissolved in 10 mL of toluene. With cooling in an ice-bath, a toluene solution (40 ml) of p-toluenesulfonyl chloride (15.94 g, 83.58 mmol) was slowly added dropwise, followed by stirring at room temperature for 1 hour. Tap water was added thereto, and the resultant layers were separated from each other. The obtained organic layer was washed with 2 M hydrochloric acid and tap water. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate=20 / 1→4 / 1). Thus, 20.25 g of the title compounds, tosylates, were obtained as a colorless oily substance. Yield: 86.2% (isomer rat...
example 3
[0070]Production of 4-methyl-N-((1S,2S)-2-(4-(4-methylcyclohexa-1,4-dienyl)butylamino)-1,2-diphenylethyl)benzenesulfonamide and 4-methyl-N-((1S,2S)-2-(4-(5-methylcyclohexa-1,4-dienyl)butylamino)-1,2-diphenylethyl)benzenesulfonamide
[0071]The tosylates (10.45 g, 32.61 mmol, isomer ratio: 1,4 type / 1,5 type=77 / 23) obtained in Example 2 were dissolved in 40 ml of toluene, and DIPEA (4.79 g, 32.61 mmol) and (S,S)-TsDPEN (11.95 g, 32.61 mmol) were added thereto, followed by stirring at 135° C. for 14 hours. After that, the solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate=2 / 1). Thus, 9.31 g of the title compounds were obtained as a yellow oily substance. Yield: 55.5% (isomer ratio: 1,4 type / 1,5 type=77 / 23). Note that the following NMR spectrum data are those of the isomer mixture.
[0072]1H NMR (CDCl3, 300 MHz): δ 7.38-7.36 (m, 2H+2H′), 7.14-7.12 (m, 3H+3H′), 7.05-7.00 (m, 5H+5H′), 6.96-6.88 (m, 4H+4...
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