Manganese complex and preparation method and application thereof
A manganese complexation and reaction technology, which is applied in the preparation of hydroxyl compounds, organic compounds, organic chemical methods, etc., can solve the problems of unreached activity, selectivity and applicable substrate range, and achieve low cost and high catalytic activity. High and stable performance
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Embodiment 1
[0032] Embodiment 1 Ligand shown in preparation formula A (R C , S P )-N-5,6,7,8-tetrahydroquinolinyl-1-(2-diphenylphosphino)ferrocenylethylamine
[0033]
[0034] 5,6,7,8-tetrahydroquinolin-(5H)-one (0.30g, 2.0mmol), (R C , S P )-1-(2-diphenylphosphino)ferrocenylethylamine (0.72g, 1.7mmol, 0.9eq) and sodium triacetoxyborohydride (1.84g, 8.0mmol, 4eq) under nitrogen Put into a round-bottomed flask, and stir the contents in 30 mL of anhydrous 1,2-dichloroethane (DCE) at 30°C for 6 h, N 2 Protect. with saturated NaHCO 3 After the solution was quenched, the mixture was extracted with ethyl acetate (3 x 30 mL), the organic phase was separated, washed with water (2 x 50 mL) and dried over anhydrous MgSO 4 . After filtration, the mixture was evaporated under reduced pressure to give a solid residue, which was purified by chromatography on silica gel with petroleum ether / ethyl acetate (v / v=1:10) as eluent. The title ligand was obtained as a pale yellow powder (0.50 g, 52%)....
Embodiment 2
[0040] Embodiment 2 (R shown in the preparation formula B C , S P )-N-5,6,7,8-tetrahydroquinolinyl-1-(2-diphenylphosphino)ferrocenylethylamine manganese complex
[0041]
[0042] Mn(CO) 5 Br (67.0mg, 0.24mmol) and (R C , S P )-N-5,6,7,8-tetrahydroquinolinyl-1-(2-diphenylphosphino)ferrocenylethylamine (150.0 mg, 0.27 mmol) was added to a round bottom flask, Add 20 mL of anhydrous toluene under nitrogen and stir the reaction at 110° C. for 16 h. The reaction mixture was cooled to room temperature and concentrated in vacuo. The residue was dissolved in dichloromethane (3 mL). n-Hexane (50 mL) was added and the solution above the precipitate was carefully removed by pipette. The precipitate was washed twice again in a similar manner with petroleum ether (2 x 50 mL), then dried under reduced pressure to afford Mn-1 as a yellow solid (160.0 mg, 90%). The structure was confirmed by NMR, X-single crystal diffraction and elemental analysis, and the confirmed data are as foll...
Embodiment 3
[0048] Example 3 Utilize (R C , S P )-N-5,6,7,8-tetrahydroquinolinyl-1-(2-diphenylphosphino)ferrocenylethylamine manganese complex as catalyst, potassium tert-butoxide as cocatalyst, Catalytic asymmetric hydrogenation of acetophenone in isopropanol, the chemical reaction formula and results are shown in Table 1 below.
[0049] Table 1 Optimization of chiral phenylethanol for stereoselective reduction of p-acetophenone
[0050]
[0051] a Experimental conditions: acetophenone (1mmol), [Mn] (1-2%mol), potassium tert-butoxide (10-20%mmol), isopropanol (30mL). Temperature (0-82℃). b The yield of acetophenone was determined by GC. c ee was measured using chiral HPLC.
[0052] It can be seen from the table that the optimal reaction conditions are: in isopropanol, the temperature is 20°C, and the S / C is 50.
[0053] a) Acetophenone (120mg, 1.0mmol) and potassium tert-butoxide (22mg, 0.2mmol) and catalyst (7mg, 0.01mmol) were successively added into a 50ml round-bottomed flas...
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