Calix[4]squaramide cyclohexanediamine derivative and method for catalyzing asymmetric Michael addition and acetalization tandem reaction by using derivative
A cyclohexanediamine, series reaction technology, applied in the field of catalytic organic synthesis, can solve the problems of low catalytic efficiency, difficult catalyst preparation, etc., and achieve the effects of high catalytic efficiency, mild synthesis process conditions, and broad industrial application prospects.
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Embodiment 1
[0023] The present embodiment is the preparation method of calix [4] squaramide cyclohexanediamine catalyst I, and the specific synthetic method is as follows:
[0024] Synthesis of Calix[4]Squaramide Cyclohexanediamine Catalyst I
[0025]
[0026] 1a (0.339g, 0.5mmol) and dimethyl squarylate (0.149g, 1.05mmol) were heated to reflux in 8mL of MeOH solution, and the reaction process was tracked by TLC. After the raw materials disappeared, the reaction was stopped, and the solvent was evaporated to obtain the crude product Separation and purification by column chromatography (ethyl acetate: petroleum ether = 1:10) gave light yellow solid 2a (0.369 g, yield 82%).
[0027] 2a.mp:>300℃; 1 H NMR (300MHz, DMSO-d 6 ): δ=0.97(t, J=6.9Hz, 12H), 1.39-1.46(m, 8H), 1.82-1.90(m, 8H), 3.13(d, J=13.5Hz, 4H), 3.78-3.87( m, 8H), 4.33(d, J=12.6Hz, 4H), 6.57-6.76(m, 10H), 10.33(s, 2H). 13 C NMR (75MHz, DMSO-d 6 ):14.4,19.3,19.4,30.8,32.2,32.3,60.8,75.0,120.0,122.4,128.4,132.2,134.4,135.8,...
Embodiment 2
[0031] In this embodiment, 2-oxo-4-phenylbut-3-enoic acid ethyl ester and 1,3-cyclohexanedione are used as substrates to catalyze the calix [4] square amide cyclohexanediamine derivative I The main influencing factors of the cascade reaction of asymmetric Michael addition and acetalization, such as solvent type, reaction temperature, reaction time, and catalyst dosage, were systematically studied.
[0032]
[0033] HPLC analysis method of product:
[0034]High performance liquid chromatography: Shimadzu LC-20A; Chromatographic column: Chiralcel OD-H (Daicel, 250mm×4.6mm, 5μm) silica gel coated with cellulose-tris(3,5-xylylcarbamate) ) chiral chromatography column; mobile phase: n-hexane / isopropanol; detection wavelength: 254nm; flow rate: 0.7mL / min; injection volume: 10μL; column temperature: 25°C.
[0035] Table 1 shows the effect of solvent on the series reaction of asymmetric Michael addition and acetalization catalyzed by calix[4]squaramide cyclohexanediamine derivativ...
Embodiment 3
[0049] In this example, referring to the best experimental conditions in Example 3, the scope of application of unsaturated ketoesters in the series reaction of asymmetric Michael addition and acetalization catalyzed by calix[4]squaramide cyclohexanediamine I was investigated.
[0050] The experimental method is: add unsaturated ketoester (0.5mmol), 1,3-cyclohexanedione (0.55mmol) and calix[4] squaramide cyclohexanediamine derivative I (0.0125mmol) to the container In a test tube of 4mL dichloromethane, magnetically stirred, the reaction solution was reacted at 25°C, the reaction time was 2 to 8 hours, and the TLC plate was used to track the reaction process until the raw materials disappeared. After the reaction, the organic phase was concentrated and passed through silica gel column chromatography. The obtained compound was isolated and purified (ethyl acetate and petroleum ether), and the optical selectivity (ee) of the product was analyzed by HPLC. The experimental results...
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