Chiral vicinal diamine derivative and catalytic asymmetric synthesis method thereof
A technology of chiral phosphoric acid and compounds, applied in organic chemistry methods, organic chemistry, etc., can solve problems such as unfavorable amine conversion, easy oxidation of alkylamines, poisoning of transition metal catalysts, etc., achieve mild reaction conditions, wide substrate range, Effect of excellent functional group tolerance
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[0049] Example 1
[0050] 1m synthesis
[0051] S-1m can be carried out according to the procedure reported in literature 2.
[0052]
[0053] At 0℃, to the stirring S-1m (2.0mmol) and iPr 2 NEt (2.0mmol) anhydrous CH 2 Cl 2 (4.0 mL) was slowly added 1-isocyanato-3,5-bis(trifluoromethyl)-benzene (2.0 mmol) to the solution. The reaction mixture was then warmed to room temperature and stirred for 1 hour. After complete conversion (monitored by TLC), the crude mixture was passed through silica gel column chromatography (eluent: petroleum ether / CH 2 Cl 2 =100 / 1 to 1 / 2, first remove CH with 100% petroleum ether 2 Cl 2 For sample loading) direct purification to obtain 1m (1.72 mmol, 86% yield).
[0054] 1 H NMR(500MHz, CDCl 3 )δ7.70(s,3H),7.41(s,1H),7.34(dd,J=5.0,3.5Hz,2H),7.31-7.26(m,2H),7.26-7.20(m,1H),5.49 (s, 1H), 5.25 (d, J = 0.5 Hz, 1H), 5.01 (d, J = 1.0 Hz, 1H), 3.23 (dd, J = 13.0, 7.5 Hz, 2H), 2.51 (t, J = 7.5Hz, 2H), 1.73–1.59 (m, 2H).
[0055] 13 C NMR(125MHz, CDCl 3 )δ155.6,147...
Example Embodiment
[0058] Example 2
[0059] Synthesis of 1n and 1l
[0060] S-1n-1 and S-1o-1 can be based on literature 3 ( C.; Hennecke, U. Org. Lett. 2015, 17, 3226).
[0061]
[0062] At 0℃, to S-1n-1 (0.57g, 3.0mmol), phthalimide (0.44g, 3.0mmol) and PPh 3 (0.79 g, 3.0 mmol) in 20.0 mL of THF was added diethyl azodicarboxylate (0.5 mL, 3.0 mmol). The mixture was warmed to room temperature for 18 hours, the solvent was extracted and purified by silica gel column chromatography (eluent: petroleum ether / EtOAc=20:1~5:1) to obtain S-1n-2 (0.8g, 83%) .
[0063] To a solution of S-1n-2 (0.64 g, 2.0 mmol) in EtOH (15.0 mL) was added hydrazine monohydrate (0.4 mL, 6.0 mmol) at room temperature. The reaction mixture was stirred and heated to reflux for 2 hours. After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated in vacuo to obtain the crude amine, which was used in the next step without purification.
[0064] 1n and 1l are obtained by similar steps to lm.
[0065...
Example Embodiment
[0079] Example 3
[0080] Synthesis of 1w and 1x
[0081]
[0082] S-1w can be carried out according to the steps reported in Literature 1 and Literature 2.
[0083] Under argon protection, neopentyl glycol (36.0 mmol) and PPTS (1.98 mmol) were added to a toluene (24.0 mL) solution of S-1w (12.0 mmol). The reaction was then stirred at 100°C for 18 hours. After complete conversion (monitored by TLC), the reaction mixture was extracted with EtOAc. The combined organic phase was concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / EtOAc=20 / 1) to obtain S-1x (10.8 mmol, 90% yield).
[0084] At 0℃, to LiAlH 4 (456.0mg, 12.0mmol) of Et 2 S-1x (6.0mmol) Et was slowly added to O (36.0mL) suspension 2 O (4.0 mL) solution. The mixture was then warmed to room temperature and stirred for 3 hours. At 0℃, slowly add water (1mL) and Na in batches 2 SO 4 (8.0 g) mixture to quench the reaction. The reaction mixture was warmed to room temperature, s...
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