Method for asymmetrically synthesizing lycoris alkaloid (+)-gamma-lycorane
A technology of Amaryllidaceae and alkaloids, which is applied in the field of asymmetric synthesis of Amaryllidaceae alkaloids-γ-lycorane, can solve the problems of complicated steps, unfavorable alkaloid synthesis and biological activity, etc., and achieves simple operation process and good technical support. , the effect of a short synthetic route
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Embodiment 1
[0067] Synthesis of formula (3) compound
[0068]
[0069] The compound of formula (2) (4.0g, 10.95mmol, 1.0equiv) was dissolved in trifluoroacetic acid (5ml), and the reaction device was placed at room temperature for 3h. Remove trifluoroacetic acid by rotary evaporation under reduced pressure, then dissolve it with dry acetonitrile (110ml), and add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride successively to the system (4.2g, 21.90mmol, 2.0equiv) and N-hydroxy-7-azobenzotriazole (2.96g, 21.90mmol, 2.0equiv) and 2-iodopiperbenzoic acid (4.80g, 16.43mmol, 1.5equiv ) in acetonitrile mixed solvent at room temperature in reaction 2d. Spin out the organic solvent, add ethyl acetate to dissolve, and add saturated copper sulfate to stir for 10min, then extract three times with ethyl acetate, combine the organic phases, and perform column chromatography purification (petroleum ether:ethyl acetate=1:10) to obtain a white Compound of formula (3) as a solid (2.65 g, ...
Embodiment 2
[0072] Synthesis of formula (4) compound
[0073]
[0074] Formula (3) (2.26g, 4.68mmol, 1.0equiv) was dissolved in dry dichloromethane (200ml), and iodobenzene acetate (3.01g, 9.36mmol, 2.0equiv) and iodine (237.6 mg, 0.936mmol, 0.2equiv), the reaction device was placed in an ice bath at 0°C, and reacted for 2h under the illumination of a 200W tungsten lamp, and trifluoroacetic acid (4ml) and triethylsilane were added to the system Hydrogen (2.72g, 23.4mmol, 5.0equiv), the reaction device was moved to room temperature for 2h. Dichloromethane was removed by rotary evaporation under reduced pressure, and purified by column chromatography (petroleum ether: ethyl acetate = 1:1) to obtain the compound of formula (4) (1.37 g, 67%) as a white solid.
[0075] The detection data of formula (4) compound is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.15(s,1H),6.71(s,1H),6.60(m,1H),6.48(m,1H),5.96(s,2H),5.12(d,J=4.8Hz,1H), 4.59(dd,J=9.1,3.5Hz,1H),4.27–4.25(m,1H),3.36–3.25(m,2H),2.76(t...
Embodiment 3
[0077] Synthesis of formula (5) compound
[0078]
[0079] The compound of formula (4) (440.0mg, 1.0mmol, 1.0equiv) was dissolved in toluene (5ml), and the antioxidant 2,6-p-di-tert-butyl-p-cresol (1.45g, 6.6mmol, 6.6 equiv) and potassium fluoride (191.73mg, 3.3mmol, 3.3equiv). The reaction was placed under microwave conditions at 150°C for 4h. The reactor was cooled to room temperature, the toluene was spin-dried in vacuo, and purified by column chromatography (petroleum ether: ethyl acetate = 2:1) to obtain the compound of formula (5) (217.45 mg, 55%) as a pale yellow solid.
[0080] The detection data of formula (5) compound is as follows: rotamer A: 1 H NMR (400MHz, CDCl 3 )δ7.19(s,1H),6.74(s,1H),6.09–5.76(m,6H),5.05–5.03(m,1H),3.61–3.55(m,1H),3.12–3.06(m, 1H),2.90–2.77(m,1H),2.16–2.09(m,1H),2.01–1.90(m,1H); 13 C NMR (100MHz, CDCl 3 )δ168.4, 148.6, 148.5, 137.1, 127.6, 124.1, 122.7, 122.6, 118.5, 107.3, 101.9, 80.9, 55.6, 46.2, 36.3, 31.8.rotamer B: 1 H NMR (400M...
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