Ethyl-Trger's base derivative as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an ethyl-# imgabs0 # base derivative as well as a preparation method and application thereof. The ethyl-# imgabs1 # base derivative provided by the invention is a compound with a structure as shown in a formula I: # imgabs2 #. The compound provided by the invention is an enantiomer-pure ethyl-# imgabs3 # base compound, has a nitrogen chiral center and a unique rigid structure, and can be used for preparing a compound with a nitrogen chiral center. And a material structure basis can be provided for molecular recognition, supramolecular chemistry, asymmetric catalysis and discovery of novel drug molecules. Particularly, the compound provided by the invention can be used as a chiral catalyst to catalyze aziridine propanation reaction of chalcone, and the whole reaction condition is mild, the yield is moderate, the enantioselectivity is moderate, and the compound is suitable for being used as the chiral catalyst.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic chemical synthesis and specifically relates to an ethyl- Base derivatives and preparation methods and applications thereof. Background Art

[0002] In the field of central chirality research, the research on central chiral carbon is relatively mature. However, the research on other chiral atoms such as nitrogen chiral centers is still relatively scarce. The reason is that the lone pair of electrons on the nitrogen atom is very easy to flip and cause racemization. Therefore, the catalytic asymmetric synthesis of compounds containing nitrogen chiral centers is extremely challenging.

[0003] Base is a special structure with a nitrogen chiral center, the classic The methylene bridge in the base molecule is connected to the benzene ring in an almost vertical manner, which prevents the lone pair of electrons on the chiral nitrogen atom from flipping. Base is a nitrogen chiral molecule with a C2 symmetry axis and a hydrophobic cavity. The base has two chiral nitrogen atoms and a unique rigid structure, which has attracted the attention of more and more researchers. Base derivatives have been successfully applied in frontier fields such as DNA chiral recognition, supramolecular chemistry, material chemistry, asymmetric catalysis and drug development. There are few types of base derivatives, and there is also a lack of simple and fast synthesis The preparation process of base derivatives limits Further applications of base derivatives in many fields. Summary of the invention

[0004] In order to solve the above technical problems, the first object of the present invention is to provide an ethyl- Base derivatives are nitrogen chiral molecules with unique three-dimensional structures and unique rigid structures, which can provide a structural basis for molecular recognition, supramolecular chemistry, asymmetric catalysis and the discovery of new drug molecules.

[0005] The second object of the present invention is to provide the above-mentioned ethyl- The preparation method of base derivatives has simple process and is convenient for industrial application.

[0006] The third object of the present invention is to provide the above-mentioned ethyl- Application of base derivatives, the nitrogen chiral compound can be used as a chiral catalyst to catalyze asymmetric aziridine reaction.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] An ethyl- Base derivatives are compounds with the structure shown in Formula I:

[0009]

[0010] In Formula I, Ar 1 ,Ar 2 is an aryl group containing a substituent;

[0011] Among them, Ar 1 The substituent in is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy; Ar 2 The substituents are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy, and trimethylsilyl.

[0012] Based on the synthesis yield and application effect of nitrogen chiral compounds, as a preferred solution, the ethyl- Base derivatives are compounds Ⅰ-1 to Ⅰ-20 with the following structures:

[0013]

[0014]

[0015] The above ethyl- The preparation method of base derivatives comprises the following steps:

[0016]

[0017] Compound 1, compound 2 and an inorganic base are mixed in an organic solvent, and then subjected to a bisallylation substitution reaction under the action of metal palladium and a chiral ligand to obtain an ethyl- Base class derivatives.

[0018] As a preferred solution, the inorganic base is one of sodium carbonate, potassium carbonate and cesium carbonate. Further preferably, the inorganic base is sodium carbonate.

[0019] As a preferred solution, the organic solvent is one or more of chloroform, methane, dichloromethane, and tetrahydrofuran. Further preferably, the organic solvent is chloroform.

[0020] As a preferred embodiment, in the compound 2, R is one of methyl, ethyl, tert-butyl, and benzyl, and is more preferably methyl.

[0021] As a preferred solution, the metal palladium is Pd2(dba)3·CHCl3; the chiral ligand is N,N-bis((S)-1-phenylethyl)-4,5,6,7-tetrahydrobiindeno[7,1-de:1',7'-fg][1,3,2]dioxaphosphooctacyclic-12-amine.

[0022] As a preferred solution, the temperature of the bisallyl substitution reaction is 50-70°C and the time is 20-40 hours. As a preferred solution, the molar ratio of compound 1, compound 2, inorganic base, metal palladium and chiral ligand during the reaction is 1: (1.4-1.6): (1.8-2.2): (0.04-0.06): (0.14-0.16). As a further preferred solution, the molar ratio of compound 1, compound 2, inorganic base, metal palladium and chiral ligand during the reaction is 1: 1.5: 2: 0.05: 0.15. The above-mentioned ethyl- The application of base derivatives as chiral catalysts in catalytic aziridine reactions.

[0023] As a preferred solution, the aziridination reaction is an aziridination reaction of chalcone. The above technical solution of the present invention has the following advantages over the prior art:

[0024] The present invention provides ethyl- Base derivatives, enantiomerically pure ethyl- Base compounds, which have nitrogen chiral centers and unique rigid structures, can provide the material structural basis for molecular recognition, supramolecular chemistry, asymmetric catalysis and the discovery of new drug molecules.

[0025] The present invention provides ethyl- The preparation method of base derivatives is based on a simple and easily available tetrahydrodibenzodiazepine compound, and a palladium-catalyzed asymmetric bisallyl alkyl substitution reaction is used to obtain a target compound with nitrogen chirality. The entire process is simple to operate, and the compound structure is easy to modify, which is convenient for mass production and commercial application. The application of base derivatives, the applied compounds have nitrogen chiral centers and can be used as chiral catalysts to catalyze the aziridine reaction of chalcone. The entire reaction conditions are mild, the yield is moderate, and the enantioselectivity is moderate. It is suitable for application as a chiral catalyst and can also provide a structural basis for the development of new catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The compound Ⅰ-1 obtained in Example 1 of the present invention 1 H NMR result diagram;

[0027] Figure 2 The compound I-1 obtained in Example 1 of the present invention 13 C NMR result diagram;

[0028] Figure 3 The compound I-2 obtained in Example 2 of the present invention 1 H NMR result diagram;

[0029] Figure 4 The compound I-2 obtained in Example 2 of the present invention 13 C NMR result diagram;

[0030] Figure 5 The compound I-3 obtained in Example 3 of the present invention 1 H NMR result diagram;

[0031] Figure 6 The compound I-3 obtained in Example 3 of the present invention 13 C NMR result diagram;

[0032] Figure 7 The compound I-4 obtained in Example 4 of the present invention 1 H NMR result diagram;

[0033] Figure 8 The compound I-4 obtained in Example 4 of the present invention 13 C NMR result diagram;

[0034] Fig. 9 The compound I-5 obtained in Example 5 of the present invention 1 H NMR result diagram;

[0035] Fig.10 The compound I-5 obtained in Example 5 of the present invention 13 C NMR results. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with the accompanying drawings and specific examples so that those skilled in the art can better understand the present invention and implement it, but the examples are not intended to limit the present invention. The test methods used in the following examples are conventional methods unless otherwise specified; the raw materials used are commonly used in the art, available to the public or commercially available unless otherwise specified.

[0037] In the present invention, the abbreviations of substituents have the meanings commonly understood in the art, such as "Me" refers to methyl, "Et" refers to ethyl, n Pr" is n-propyl, i Pr" is isopropyl, n Bu" is n-butyl, t "Bu" means tert-butyl, n "Am" is n-pentyl, "Bn" is benzyl, "H" is hydrogen, "F" is fluorine, "Cl" is chlorine, "Br" is bromine, "MeO" is methoxy, "BnO" is benzyloxy, "TMS" is trimethylsilyl, and "Ph" is phenyl.

[0038] The ethyl- Base derivatives are compounds with the structure shown in Formula I:

[0039]

[0040] In Formula I, Ar 1 ,Ar 2 is an aryl group containing a substituent;

[0041] Among them, Ar 1 The substituent in is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy; Ar 2 The substituents are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy, and trimethylsilyl.

[0042] Specifically, in Examples 1 to 20 provided below, ethyl- The preparation method of base derivatives adopts the following technical route:

[0043]

[0044] The ethyl- Base derivatives are recorded as compounds I-1 to I-20. In the following examples, the metal palladium used is Pd2(dba)3·CHCl3; the chiral ligand is N,N-bis((S)-1-phenylethyl)-4,5,6,7-tetrahydrobiindeno[7,1-de:1',7'-fg][1,3,2]dioxaphosphat-12-amine.

[0045] In the following examples, R in compound 2 is one of methyl, ethyl, tert-butyl, and benzyl, preferably methyl. In the following examples 1 to 20, the raw material compound 1 used is a tetrahydrodibenzodiazepine compound, which is sequentially recorded as compound 1a to compound 1t, which can be conventionally prepared by referring to the following prior art:

[0046] [1]Functionalized analogues of base:scope and limitations of ageneral synthetic procedure and facility,predictable method for the separation of enantiomers.DOI:10.1016 / j.tet.2008.04.111;

[0047] [2]Synthesis of 5,6,11,12-tetrahydrodibenzo[b,f][1,5]diazocines and ademonstration of their reactivity to afford methano strap-modified base analogues.DOI:10.3998 / ark.5550190.0009.c17.

[0048] Example 1 This example provides an ethyl- The base derivative, denoted as compound I-1, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound comprises the following steps: taking a 10 mL schlenk tube, adding compound 1a (in compound 1a, Ar 1 =Ar 2=4-MePh, added amount 23.8mg, 0.1mmol, 1.0equiv), compound 2 (R = Me, 30mg, 0.15mmol, 1.2equiv), sodium carbonate (20mg, 0.2mmol, 2.0equiv), then added 2mL of anhydrous chloroform, followed by nitrogen replacement operation, metal palladium (5mg, 0.005mmol, 0.05equiv) and chiral ligand (15mg, 0.015mmol, 0.15equiv) were added to the reaction bottle under nitrogen protection, and the reaction was carried out at 60°C for 24 hours. 3mL of saturated ammonium chloride solution was added to the reaction system to terminate the reaction, and dichloromethane was extracted three times (3×6mL). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography, and the developing solvent was ethyl acetate / petroleum ether = 30 / 1 to obtain compound I-1 (Ar 1 =Ar 2 =4-MePh) 24.7 mg, the yield is 85%, the state is colorless oily liquid.

[0049] The analytical data of the product are as follows: optical rotation value: -344.01 (concentration is 0.45, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.63 min, peak time 2 is 4.79 min, and enantioselectivity is 96%.

[0050] NMR of compound I-1 obtained in Example 1 1 H NMR, 13 C NMR spectra are shown in Figure 1 , Figure 2 As shown. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.05(d,J=8.0Hz,1H),6.96(d,J=8.0Hz,1H),6.93-6.82(m,2H),6.71(s,1H),6.63(s,1H),6.07-5.90(m,1H),5.24-5.14(m, 1H),5.08-4.96(m,1H),4.67(d,J=17.3Hz,1H),4.50(d,J=17.5Hz,2H),4 .35(d,J=17.3Hz,1H),4.30-4.23(m,1H),3.89-3.74(m,2H),2.17(s,6H). 13C NMR (100 MHz, CDCl3) δ 147.4, 143.9, 139.6, 137.0, 136.8, 134.7, 134.4, 129.7, 129.0, 128.5, 128.1, 127.9, 127.8, 114.9, 77.4, 77.0, 76.7, 67.2, 61.0, 60.6, 58.8, 20.8, 20.7. The high resolution characterization results are as follows: HRMS (ESI) m / z calcd for C 20 H 22 N2[M+H] + =291.1856,found=291.1856.

[0051] Example 2 This example provides an ethyl- The base derivative, denoted as compound I-2, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound has the same steps as those in Example 1, except that the compound 1a in Example 1 is adjusted to compound 1b (in compound 1b, Ar 1 =Ar 2 =4-EtPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-2 (Ar 1 =Ar 2 =4-EtPh) 28.9 mg. The yield is 91%, and the state is colorless oily liquid.

[0052] The analytical data of the product are as follows: optical rotation value: -270.19 (concentration is 0.5, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.51 min, peak time 2 is 4.79 min, and enantioselectivity is 94%.

[0053] NMR of compound I-2 obtained in Example 2 1 H NMR, 13 C NMR spectra are shown in Figure 3 , Figure 4 As shown. NMR characterization results: 1H NMR (400MHz, CDCl3) δ7.08(d,J=8.0Hz,1H),7.00(d,J=8.0Hz,1H),6.91(t,J=8.5Hz,2H),6. 73(s,1H),6.65(s,1H),6.08-5.85(m,1H),5.18(d,J=17.5Hz,1H),5.00(d,J=10.8Hz,1H),4 .70(d,J=17.4Hz,1H),4.52(dd,J=17.4,4.9Hz,2H),4.38(d,J=17.2Hz,1H),4.28(t,J=5.4H z,1H),3.90-3.81(m,1H),3.77(d,J=15.3Hz,1H),2.49(q,J=7.5Hz,4H),1.19-1.02(m,6H). 13 C NMR (100 MHz, CDCl3) δ 147.6, 144.0, 140.9, 140.7, 139.7, 137.0, 136.9, 129.8, 128.0, 127.7, 127.1, 126.7, 126.6, 114.8, 67.3, 61.1, 60.7, 58.9, 28.2, 28.1, 15.3, 15.0. High resolution characterization results are: HRMS (ESI) m / z calcd for C 22 H 26 N2[M+H] + =319.2169,found=319.2169.

[0054] Example 3 This example provides an ethyl- The base derivative, denoted as compound I-3, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1c (in Compound 1c, Ar 1 =Ar 2 =4- n PrPh), and the remaining steps were the same as in Example 1. The product obtained was compound I-3 (Ar 1 =Ar 2 =4- n PrPh) 30.4 mg. The yield is 88%, and the state is colorless oily liquid.

[0055] The analytical data of the product are as follows: optical rotation value: -19.58 (concentration is 0.32, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.42 min, peak time 2 is 3.99 min, and enantioselectivity is 97%.

[0056] Example 3 NMR of compound I-3 obtained 1 H NMR, 13 C NMR spectra are shown in Figure 5 , Figure 6 As shown. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.06(d,J=8.0Hz,1H),6.98(d,J=8.0Hz,1H),6.87(dd,J=12.7,4.7Hz,2 H),6.71(s,1H),6.63(s,1H),6.04-5.87(m,1H),5.17(d,J=17.4Hz,1H),4.99(d,J=10.7Hz,1H ),4.69(d,J=17.3Hz,1H),4.57-4.45(m,2H),4.37(d,J=17.3Hz,1H),4.30-4.22(m,1H),3.92- 3.81(m,1H),3.76(d,J=14.9Hz,1H),2.47-2.36(m,4H),1.58-1.49(m,4H),0.90-0.83(m,6H). 13 C NMR (100 MHz, CDCl3) δ 147.6, 144.0, 139.7, 139.5, 139.2, 137.0, 136.8, 129.7, 128.3, 127.8, 128.7, 127.3, 127.2, 114.8, 67.3, 61.1, 60.7, 59.0, 37.5, 37.4, 24.4, 24.2, 14.0. The high resolution characterization results are as follows: HRMS (ESI) m / z calcd for C 24 H 30 N2[M+H] + =347.2482,found=347.2487.

[0057] Example 4 This example provides an ethyl- The base derivative, denoted as compound I-4, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1d (in Compound 1d, Ar 1 =Ar 2 =4- i PrPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-4 (Ar 1 =Ar 2 =4- i PrPh) 31.1 mg. The yield is 90%, and the state is colorless oily liquid.

[0058] The analytical data of the product are as follows: optical rotation value: -46.00 (concentration is 0.10, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane=30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.42 min, peak time 2 is 4.57 min, and enantioselectivity is 97%.

[0059] NMR of compound I-4 obtained in Example 4 1 H NMR, 13 C NMR spectra are shown in Figure 7 , Figure 8 The NMR characterization results of compound I-4 are as follows: 1 H NMR (400MHz, CDCl3) δ7.08(d,J=8.1Hz,1H),7.01(d,J=8.1Hz,1H),6.94(t,J=7.6Hz,2H),6 .75(s,1H),6.67(s,1H),6.03-5.85(m,1H),5.17(d,J=17.4Hz,1H),4.99(d,J=10.7Hz,1H), 4.70(d,J=17.4Hz,1H), 4.53(dd,J=17.4,7.6Hz,2H), 4.40(d,J=17.3Hz,1H), 4.27(t,J=5. 6Hz,1H),3.91-3.80(m,1H),3.75(d,J=14.8Hz,1H),2.82-2.69(m,2H),1.21-1.10(m,12H). 13C NMR (100 MHz, CDCl3) δ 147.6, 145.5, 145.3, 139.8, 137.1, 137.0, 129.9, 128.0, 126.2, 125.7, 125.1, 125.0, 114.8, 67.3, 61.1, 60.8, 59.1, 33.4, 33.3, 24.0, 23.9, 23.8, 23.7. The high resolution characterization results are: HRMS (ESI) m / z calcdfor C 24 H 30 N2[M+H] + =347.2482,found=347.2487.

[0060] Example 5 This example provides an ethyl- The base derivative, denoted as compound I-5, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1e (in Compound 1e, Ar 1 =Ar 2 =4- n BuPh), and the remaining steps were the same as in Example 1. The product obtained was compound I-5 (Ar 1 =Ar 2 =4- n BuPh) 28.1 mg. The yield is 75%, and the state is colorless oily liquid.

[0061] The analytical data of the product are as follows: optical rotation value: -20.40 (concentration is 0.25, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane=30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.42 min, peak time 2 is 3.92 min, and enantioselectivity is 94%.

[0062] Example 5 Nuclear magnetic resonance of compound I-5 1 H NMR, 13 C NMR spectra are shown in Fig. 9 , Fig.10 As shown. NMR characterization results: 1H NMR(400MHz, CDCl3)δ6.98(d,J=8.0Hz,1H),6.90(d,J=8.0Hz,1H),6.83-6.77(m,2H),6.63(s,1H) ,6.55(s,1H),5.96-5.77(m,1H),5.09(d,J=17.4Hz,1H),4.92(d,J=10.7Hz,1H),4.61(d,J=17.3H z,1H),4.44(d,J=19.3Hz,2H),4.29(d,J=17.2Hz,1H),4.23-4.17(m,1H),3.83-3.73(m,1H),3.68 (d,J=14.8Hz,1H),2.38-2.32(m,4H),1.46-1.37(m,4H),1.23-1.17(m,4H),0.80(t,J=7.3Hz,6H). 13 C NMR (100 MHz, CDCl3) δ 147.5, 144.0, 139.7, 139.7, 139.5, 137.0, 136.8, 129.7, 128.2, 127.9, 127.6, 127.2, 127.1, 114.8, 67.3, 61.1, 60.7, 59.0, 35.0, 33.5, 33.3, 22.5, 22.5, 14.0. The high resolution characterization results are as follows: HRMS (ESI) m / z calcd for C 26 H 34 N2[M+H] + =375.2795,found=375.2800.

[0063] Example 6 This example provides an ethyl- The base derivative, denoted as compound I-6, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1f (in Compound 1f, Ar 1 =Ar 2 =4- t BuPh), and the remaining steps were the same as in Example 1. The product obtained was compound I-6 (Ar 1 =Ar 2 =4- t BuPh) 30.3 mg. The yield is 81%, and the state is colorless oily liquid.

[0064] The analytical data of the product are as follows: optical rotation value: -79.64 (concentration is 0.3, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.36 min, peak time 2 is 4.41 min, and enantioselectivity is 96%.

[0065] The following compounds of the present invention involve many NMR spectra, which will not be described in detail here. The following is only an explanation of the NMR characterization results. NMR characterization results of compound I-6: 1 H NMR (400MHz, CDCl3) δ7.17-7.06(m,3H),7.02(d,J=8.3Hz,1H),6.89(d,J=2.0Hz,1 H),6.81(d,J=0.9Hz,1H),5.99-5.85(m,1H),5.16(d,J=17.4Hz,1H),5.04-4.94(m ,1H),4.72(d,J=17.4Hz,1H),4.54(dd,J=17.4,8.3Hz,2H),4.41(d,J=17.2Hz,1H) ,4.30-4.22(m,1H),3.88-3.79(m,1H),3.77-3.70(m,1H),1.22(d,J=3.0Hz,18H). 13 C NMR (100 MHz, CDCl3) δ 147.9, 147.6, 147.3, 143.7, 139.8, 136.7, 136.6, 129.6, 127.8, 124.9, 124.4, 124.2, 124.1, 114.8, 67.35, 61.27, 60.9, 59.2, 34.2, 31.4. High resolution characterization results are: HRMS (ESI) m / z calcd for C 26 H 34 N2[M+H] + =375.2795,found=375.2800.

[0066] Example 7 This example provides an ethyl- The base derivative, denoted as compound I-7, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1g (in Compound 1g, Ar 1 =Ar 2 =4- n AmPh), and the remaining steps were the same as in Example 1. The product obtained was compound I-7 (Ar1 =Ar 2 =4- n AmPh) 31.8 mg. The yield is 79%, and the state is colorless oily liquid.

[0067] The analytical data of the product are as follows: optical rotation value: -9.4 (concentration 0.38, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.37 min, peak time 2 is 3.79 min, enantioselectivity is 93%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.06 (d, J=8.0Hz, 1H), 6.98 (d, J=8.0Hz, 1H), 6.93-6.84 (m, 2H), 6.70 (d, J= 1.3Hz,1H),6.63(d,J=1.4Hz,1H),6.03-5.84(m,1H),5.24-5.12(m,1H),5.06-4.79(m,1H),4.69( d,J=17.3Hz,1H),4.57-4.42(m,2H),4.37(d,J=17.2Hz,1H),4.31-4.22(m,1H),3.91-3.79(m,1H ),3.79-3.66(m,1H),2.49-2.37(m,4H),1.58-1.45(m,4H),1.31-1.23(m,8H),0.88-0.81(m,6H). 13 C NMR (100 MHz, CDCl3) δ 147.5, 144.0, 139.8, 139.7, 139.5, 137.0, 136.9, 129.7, 128.2, 127.9, 127.6, 127.2, 127.1, 114.8, 67.3, 61.1, 60.7, 59.0, 35.33, 31.71, 31.7, 31.0, 30.8, 22.5, 14.0. The high resolution characterization results are as follows: HRMS (ESI) m / z calcd for C 28 H 38 N2[M+Na] + =425.2928,found=425.2930.

[0068] Example 8 This example provides an ethyl- The base derivative, denoted as compound I-8, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1h (in compound 1h, Ar 1 =Ar 2 =4-BnPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-8 (Ar 1 =Ar 2 =4-BnPh) 37.6 mg. The yield is 85%, and the state is colorless oily liquid.

[0069] The analytical data of the product are as follows: optical rotation value: -749.03 (concentration 0.2, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 4.88 min, peak time 2 is 7.14 min, enantioselectivity is 96%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.27-7.21(m,4H),7.20-7.14(m,2H),7.14-7.08(m,4H),7.07-7.04(m,1H), 6.97(d,J=8.0Hz,1H),6.89-6.82(m,2H),6.71(s,1H),6.63(s,1H),5.99-5.82(m,1H),5.15(dd,J= 17.4,0.7Hz,1H),4.98(dd,J=10.8,0.9Hz,1H),4.64(d,J=17.4Hz,1H),4.48(d,J=17.4Hz,2H),4.3 3(d,J=17.3Hz,1H),4.28-4.20(m,1H),3.84(d,J=7.5Hz,1H),3.80(s,4H),3.73(d,J=14.9Hz,1H). 13 C NMR (100 MHz, CDCl3) δ 148.0, 144.5, 141.1, 140.9, 139.6, 137.9, 137.7, 137.2, 137.1, 130.1, 129.1, 129.0, 128.8, 128.5, 128.4, 128.2, 127.8, 127.7, 126.1, 115.0, 67.3, 61.0, 60.6, 58.9, 41.4, 41.3. The high resolution characterization results are: HRMS (ESI) m / z calcd for C 32 H 30 N2[M+Na] + =465.2302,found=465.2307.

[0070] Example 9 This example provides an ethyl- The base derivative, denoted as compound I-9, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1i (in compound 1i, Ar 1 =Ar 2 =Ph), and the remaining steps are the same as in Example 1. The obtained product is compound I-9 (Ar 1 =Ar 2 =Ph) 21.7 mg. The yield is 83%, and the state is colorless oily liquid.

[0071] The analytical data of the product are as follows: optical rotation value: -17.60 (concentration 0.25, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.97 min, peak time 2 is 4.77 min, enantioselectivity is 81%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.19-7.13(m,1H),7.12-7.02(m,3H),6.99-6.88(m,3H ),6.83(d,J=7.5Hz,1H),6.06-5.84(m,1H),5.27-5.12(m,1H),5.12-4.97(m, 1H),4.74(d,J=17.4Hz,1H),4.59(d,J=5.9Hz,1H),4.55(d,J=5.8Hz,1H),4.4 2(d,J=17.3Hz,1H),4.36-4.27(m,1H),3.97-3.85(m,1H),3.84-3.74(m,1H). 13 C NMR (100MHz,CDCl3)δ150.0,146.6,139.4 137.2,137.0,130.0,128.5,128.1,127.9,127.3,127.2,125.3,125.0,115.0,67.2,61.0,60.7,58.7. The high resolution characterization results are: HRMS (ESI) m / z calcd for C 18 H 18 N2[M+H] + =263.1543,found=263.1547.

[0072] Example 10 This example provides an ethyl- The base derivative, denoted as compound I-10, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1j (in Compound 1j, Ar 1 =Ar 2 =4-FPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-10 (Ar 1 =Ar 2 =4-FPh) 25.3 mg. The yield is 85%, and the state is colorless oily liquid.

[0073] The analytical data of the product are as follows: optical rotation value: -150.58 (concentration 0.35, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 4.03 min, peak time 2 is 5.24 min, enantioselectivity is 91%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.18-7.07(m,1H),7.07-6.98(m,1H),6.83-6.70(m,2H),6.61(dd,J=9.1,2.9Hz,1H),6.54(dd,J=9.0,2.9Hz,1H),6.0 1-5.83(m,1H),5.23-5.14(m,1H),5.09-4.93(m,1H),4.71-4.59(m,1H ),4.48(dd,J=17.4,3.4Hz,2H),4.36-4.24(m,2H),3.86-3.74(m,2H). 13 C NMR (100MHz, CDCl3) δ160.1 (J=243Hz), 159.4 (J=243Hz), 158.7, 145.7, 145.6, 142.2, 142.1, 139.2 (J=22Hz), 139.0 (J=24H z),131.6,131.5,129.7,129.6,115.2,114.6,114.4,114.3,114.3,114.1(J=5Hz),,114.0,113.9,67.0,60.8,60.5,58.6. 19 F NMR (376MHz,CDCl3)δ-117.52,-117.89. High resolution characterization results are: HRMS (ESI) m / z calcd for C 18 H 16 F2N2[M+H]+ =299.1355,found=299.1357.

[0074] Example 11 This example provides an ethyl- The base derivative is denoted as compound I-11, which is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1k (in compound 1k, Ar 1 =Ar 2 =4-ClPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-11 (Ar 1 =Ar 2 =4-ClPh) 23.4 mg. The yield is 71%, and the state is colorless oily liquid.

[0075] The analytical data of the product are as follows: optical rotation value: -56.06 (concentration 0.3, solvent dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 4.03 min, peak time 2 is 5.51 min, enantioselectivity is 84%. NMR characterization results: 1 H NMR (400MHz, DMSO) δ7.18-6.99(m,5H),6.95(s,1H),5.94-5.76(m,1H),5.19(d,J=17.5Hz,1H),5.06-4.92(m,1H ),4.74(d,J=17.6Hz,1H),4.46(d,J=17.7Hz,1H),4.40-4.24(m,3H),4.00-3.74(m,1H),3.69(d,J=14.8Hz,1H). 13 C NMR (100 MHz, DMSO) δ 149.4, 146.3, 139.8, 139.7, 139.4, 131.9, 130.1, 129.3, 128.9, 128.5, 127.9, 127.5, 127.3, 115.8, 66.3, 59.9, 59.8, 57.8. High resolution characterization results are: HRMS (ESI) m / z calcd for C 18 H 16 Cl2N2[M+H] + =331.0764,found=331.0760.

[0076] Example 12 This example provides an ethyl- The base derivative, denoted as compound I-12, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 11 (in Compound 11, Ar 1 =Ar 2 =4-OMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-12 (Ar 1 =Ar 2 =4-OMePh) 29.0 mg. The yield is 90%, and the state is colorless oily liquid.

[0077] The analytical data of the product are as follows: optical rotation value: -147.78 (concentration 0.3, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 4.32 min, peak time 2 is 8.36 min, enantioselectivity is 98%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.09(d,J=8.6Hz,1H),7.01(d,J=8.6Hz,1H),6.68-6.58(m,2H),6.47-6.31(m,2H),6.02-5.86(m,1H),5.17(d,J=17.5Hz,1H) ,5.00(d,J=10.8Hz,1H),4.66(d,J=17.3Hz,1H),4.48(d,J=14.8Hz,2H),4 .33(d,J=17.3Hz,1H),4.27-4.11(m,1H),3.89-3.73(m,2H),3.67(s,6H). 13 CNMR (100MHz,CDCl3)δ157.0,156.7,142.9,139.6,139.3,138.6,138.4,131.0,129.1,114.8,112.9,112.9,112.8,112.3,67.3,61.2,60.9,59.0,55.3,55.2. High resolution characterization results are: HRMS (ESI) m / zcalcd for C 20 H 22 N2O2[M+H] + =323.1755,found=323.1757.

[0078] Example 13 This example provides an ethyl- The base derivative, denoted as compound I-13, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1m (in compound 1m, Ar 1 =Ar 2 =4-OBnPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-13 (Ar 1 =Ar 2 =4-OBnPh) 43.1 mg. The yield is 91% and the state is colorless oily liquid.

[0079] The analytical data of the product are as follows: optical rotation value: -144.67 (concentration 0.3, solvent dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 5.37 min, peak time 2 is 8.93 min, enantioselectivity is 98%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.41-7.27(m,10H),7.10(d,J=8.6Hz,1H),7.01(d,J=8.6H z,1H),6.76-6.64(m,2H),6.50(dd,J=26.6,2.8Hz,2H),6.05-5.88(m,1H),5.18 (d,J=17.4Hz,1H),5.04-4.98(m,1H),4.91(d,J=5.0Hz,4H),4.66(d,J=17.4Hz, 1H),4.55-4.41(m,2H),4.33(d,J=17.3Hz,1H),4.26(s,1H),3.88-3.70(m,2H). 13 C NMR (100 MHz, CDCl3) δ 156.3, 156.1, 143.2, 139.6, 138.7, 138.5, 137.1, 137.1, 131.2, 129.1, 128.6, 128.0, 127.9, 127.6, 127.5, 114.9, 113.8, 113.7, 113.6, 113.3, 70.1, 70.0, 67.3, 61.2, 60.9, 59.0. High resolution characterization results are: HRMS (ESI) m / zcalcd for C 32 H 30 N2O2[M+H] + =475.2381,found=475.2386.

[0080] Example 14 This example provides an ethyl- The base derivative, denoted as compound I-14, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound has the same steps as those in Example 1, except that the compound 1a in Example 1 is adjusted to compound 1n (in compound 1n, Ar 1 =Ar 2 =3-MePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-14 (Ar 1 =Ar 2 =3-MePh) 25.2 mg. The yield is 87%, and the state is colorless oily liquid.

[0081] The analytical data of the product are as follows: optical rotation value: -61.24 (concentration 0.58, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 1 / 99, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 4.34 min, peak time 2 is 5.28 min, enantioselectivity is 91%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.97(s,1H),6.88(s,1H),6.82-6.64(m,4H),6.10-5.86(m,1H),5.18(d,J=17.5Hz,1H),5.00(d,J=10.8Hz,1H),4.68(d,J=17 .2Hz,1H),4.52(dd,J=17.2,7.0Hz,2H),4.38(d,J=17.1Hz,1H),4.28(t,J =5.4Hz,1H),3.93-3.82(m,1H),3.81-3.71(m,1H),2.21(d,J=5.4Hz,6H). 13 CNMR (100MHz,CDCl3)δ149.9,146.4,139.5,136.8,136.8,134.0,133.7,130.5,128.6,128.3,127.7,126.2,125.8,114.9,67.3,60.8,60.4,58.8,20.9,20.8.High resolution characterization results are: HRMS (ESI) m / zcalcd for C 20 H 22 N2[M+H] + =291.1856,found=291.1861.

[0082] Example 15 This example provides an ethyl- The base derivative, denoted as compound I-15, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1o (in compound 1o, Ar 1 =Ar 2 =3-EtPh), and the remaining steps are the same as in Example 1. The product obtained is compound I-15 (Ar 1 =Ar 2 =3-EtPh) 25.6 mg. The yield is 81% and the state is colorless oil.

[0083] The analytical data of the product are as follows: optical rotation value: -32.33 (concentration 0.3, solvent dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.73 min, peak time 2 is 4.19 min, enantioselectivity is 90%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.92 (s, 1H), 6.84 (s, 1H), 6.78-6.70 (m, 3H), 6.68 (d, J = 7.8Hz, 1 H),6.00-5.79(m,1H),5.11(d,J=17.5Hz,1H),5.01-4.85(m,1H),4.62(d,J=17.3Hz,1 H),4.46(dd,J=17.2,10.7Hz,2H),4.33(d,J=17.2Hz,1H),4.22(t,J=5.6Hz,1H),3.85 -3.75(m,1H),3.70(dd,J=14.9,0.9Hz,1H),2.46(p,J=7.6Hz,4H),1.14-1.06(m,6H). 13 C NMR (100 MHz, CDCl3) δ 149.9, 146.5, 143.2, 139.6, 134.3, 134.1, 129.2, 128.3, 127.7, 127.3, 124.9, 124.6, 114.87, 67.3, 60.8, 60.4, 58.9, 28.2, 28.1, 15.3, 15.1. High resolution characterization results are: HRMS (ESI) m / z calcdfor C 22 H 26 N2[M+H] + =319.2169,found=319.2175.

[0084] Example 16 This example provides an ethyl- The base derivative, denoted as compound I-16, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1p (in Compound 1p, Ar 1 =Ar 2 =3,4-diMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-16 (Ar 1 =Ar 2 =3,4-diMePh) 26.7 mg. The yield is 84%, and the state is colorless oily liquid.

[0085] The analytical data of the product are as follows: optical rotation value: -15.01 (concentration 0.43, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.71 min, peak time 2 is 4.06 min, enantioselectivity is 95%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.93(s,1H),6.85(s,1H),6.66(s,1H),6.58(s,1H),6.13-5. 75(m,1H),5.18(d,J=17.5Hz,1H),5.05-4.93(m,1H),4.64(d,J=17.2Hz,1H),4.50( d,J=5.7Hz,1H),4.46(d,J=5.5Hz,1H),4.34(d,J=17.1Hz,1H),4.29-4.18(m,1H), 3.88-3.79(m,1H),3.79-3.72(m,1H),2.12(d,J=3.3Hz,6H),2.07(d,J=1.1Hz,6H). 13 C NMR (100 MHz, CDCl3) δ 147.6, 144.0, 139.7, 135.3, 135.2, 134.3, 134.1, 133.4, 133.1, 130.9, 129.5, 129.0, 128.9, 114.75, 67.39, 60.7, 60.3, 59.0, 19.3, 19.3, 19.1, 19.0. The high resolution characterization results are as follows: HRMS (ESI) m / z calcd for C 22 H 26 N2[M+H] + =319.2169,found=319.2173.

[0086] Example 17 This example provides an ethyl- The base derivative, denoted as compound I-17, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1q (in Compound 1q, Ar 1 =Ar 2 =3,4-diOMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-17 (Ar 1 =Ar 2 =3,4-diOMePh) 34.0 mg. The yield is 89% and the state is colorless oily liquid.

[0087] The analytical data of the product are as follows: optical rotation value: -64.31 (concentration 0.37, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 10.54 min, peak time 2 is 11.80 min, enantioselectivity is 95%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.71(s,1H),6.63(s,1H),6.39(s,1H),6.32(s,1H),6.03-5.90(m,1H),5.18(d,J=17.5Hz,1H),5.02(d,J=10.6Hz,1H),4.67 (d,J=17.1Hz,1H),4.48(d,J=17.1Hz,2H),4.34(d,J=17.0Hz,1H),4.29- 4.19(m,1H),3.90-3.84(m,1H),3.82(d,J=5.0Hz,6H),3.78-3.70(m,7H). 13 C NMR (100 MHz, CDCl3) δ 147.8, 147.7, 146.6, 146.4, 142.5, 139.5, 138.9, 128.6, 128.3, 114.9, 112.9, 111.2, 110.4, 109.8, 67.7, 60.6, 60.3, 59.5, 55.9, 55.8, 55.7. High resolution characterization results are: HRMS (ESI) m / zcalcd for C 22 H 26 N2O4[M+H] + =383.1966,found=383.1965.

[0088] Example 18 This example provides an ethyl- The base derivative, denoted as compound I-18, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1r (in Compound 1r, Ar 1 =Ar 2 =3,5-diOMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-18 (Ar 1 =Ar 2 =3,5-diOMePh) 28.3 mg. The yield is 89% and the state is colorless oily liquid.

[0089] The analytical data of the product are as follows: optical rotation value: -23.00 (concentration 0.2, solvent dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 1 / 99, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.81 min, peak time 2 is 4.60 min, enantioselectivity is 93%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.74 (d, J = 27.4Hz, 2H), 6.62-6.49 (m, 2H), 5.93-5.69 ( m,1H),5.08(d,J=17.5Hz,1H),4.91(d,J=10.7Hz,1H),4.60(d,J=17.6Hz,1H ),4.48(d,J=17.5Hz,1H),4.37(d,J=17.6Hz,1H),4.24-4.11(m,2H),3.87-3 .71(m,1H),3.69-3.58(m,1H),2.11(d,J=3.9Hz,6H),2.00(d,J=16.3Hz,6H). 13 C NMR (100MHz,CDCl3)δ149.4,145.7,138.7,135.1,135.04,134.9,134.4,131.2,131.0,127.6,127.3,126.9,125.7,113.5,65.6,57.5,57.43,56.77,19.7,19.6,18.5,18.4. High resolution characterization results are: HRMS (ESI) m / z calcd for C 22 H 26 N2[M+H] + =319.2169,found=319.2174.

[0090] Example 19 This example provides an ethyl- The base derivative, denoted as compound I-19, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that the compound 1a in Example 1 is adjusted to compound 1s (in compound 1s, Ar 1 =Ar 2 =3,4,5-triMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-19 (Ar 1 =Ar 2 =3,4,5-triMePh) 28.7 mg. The yield is 83% and the state is colorless oily liquid.

[0091] The analytical data of the product are as follows: optical rotation value: -21.42 (concentration 0.12, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 30 / 70, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 3.51 min, peak time 2 is 3.79 min, enantioselectivity is 95%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ6.78 (s, 1H), 6.72 (s, 1H), 6.13-5.51 (m, 1H), 5.08 (d, J = 1 7.4Hz,1H),4.89(d,J=10.7Hz,1H),4.67(d,J=17.5Hz,1H),4.56(d,J=17.4Hz, 1H),4.43(d,J=17.5Hz,1H),4.23(d,J=17.4Hz,1H),4.20-4.11(m,1H),3.78-3 .68(m,1H),3.68-3.58(m,1H),2.08(s,6H),1.95(d,J=2.7Hz,9H),1.91(s,3H). 13 C NMR (100 MHz, CDCl3) δ 147.8, 143.8, 140.0, 134.9, 134.8, 134.4, 132.7, 132.6, 132.2, 131.9, 129.1, 127.2, 114.4, 66.7, 59.8, 59.1, 58.8, 20.7, 20.63, 15.5, 15.4, 15.4, 15.3. High resolution characterization results are: HRMS (ESI) m / z calcd for C 24 H 30 N2[M+H] +=347.2482,found=347.2482.

[0092] Example 20 This example provides an ethyl- The base derivative, denoted as compound I-20, is an enantiomerically pure chiral compound with the structural formula: The preparation method of the compound is basically the same as that of Example 1, except that: Compound 1a in Example 1 is adjusted to Compound 1t (in Compound 1t, Ar 1 =4-BrPh,Ar 2 =4-TMSMePh), and the remaining steps are the same as in Example 1. The product obtained is compound I-20 (Ar 1 =4-BrPh,Ar 2 =4-TMSMePh) 49.2 mg. The yield is 95%, and the state is colorless oily liquid. Among them, the product compound I-20 has diastereoisomers, so the connecting bond at H in the structural formula is temporarily represented by a wavy line.

[0093] The analytical data of the product are as follows: optical rotation value: -304.01 (concentration is 0.15, solvent is dichloromethane); HPLC (IB chiral column, isopropanol / n-hexane = 2 / 98, flow rate is 1.0 mL / min, wavelength is 254 nm), peak time 1 is 3.73 min, peak time 2 is 9.79 min, enantioselectivity is 97%; peak time 3 is 4.03 min, peak time 4 is 6.18 min, enantioselectivity is 97%; diastereoselectivity is 1:2. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ7.10-6.89(m,3H),6.90-6.80(m,2H),6.78(d,J=8.3Hz,1H),5.85-5.65(m,1H),5.08-4.91(m,1H),4.91-4. 76(m,1H),4.62-4.44(m,1H),4.40-4.28(m,2H),4.27-4.15(m,1H),4.15-4.04(m,1H),3.74-3.55(m,2H),0.00(d,J=2.6Hz,9H). 13C NMR (100 MHz, CDCl3) δ 151.4, 150.4, 147.9, 147.0, 140.7, 140.5, 140.2, 140.0, 138.3, 138.0, 136.8, 136.7, 134.7, 134.1, 133.6, 133.5, 133.0, 132.2, 131.7, 131.4, 131.2, 131.1, 130.2, 128.4, 119.2, 118.8, 116.3, 116.2, 68.2, 68.0, 61.9, 61.6, 61.5, 61.1, 59.8, 59.4, 0.0, -0.0. The high resolution characterization results are: HRMS (ESI) m / z Calculate for C 21 H 25 BrN2Si[M+H] + =413.1044,found=413.1040.

[0094] Experimental Example 1: Application Performance Test This experimental example uses the ethyl- The base derivative (Compound I-1) is used as an example to illustrate the application direction and application performance of the compound of the present invention. Other compounds prepared by the present invention can also achieve a considerable chiral catalytic effect. Specifically, the ethyl- The base derivative (Compound I-1) was used to catalyze the aziridination reaction of chalcone to investigate its catalytic effect as a chiral catalyst. The specific steps are as follows:

[0095]

[0096] Take a 50 mL round-bottom flask, add 1 mL acetonitrile, 0.5 mL dichloromethane, compound 3 (i.e. chalcone, 20.8 mg, 0.1 mmol) and the ethyl- A base derivative (compound I-1, 0.04mmol, 0.4equiv) was added, followed by the addition of 2,4,6-trimethylbenzenesulfonylhydroxylamine (MSH, 0.022g, 0.1mmol) and cesium hydroxide monohydrate (CsOH·H2O, 0.025g, 0.15mmol). After stirring for 1 hour, MSH (0.011g, 0.05mmol) and CsOH·H2O (0.0125g, 0.075mmol) were added. After further stirring for 1 hour, MSH (0.011g, 0.05mmol) and CsOH·H2O (0.0125g, 0.075mmol) were added, and then the mixture was reacted at -30°C for 24 hours. 5 mL of water was added to terminate the reaction, and the mixture was extracted with ethyl acetate (3×10 mL). The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography with a developing solvent ratio of ethyl acetate / petroleum ether = 1 / 10 to obtain the target product, compound 4, a total of 10 mg, with a yield of 45%, as a white solid.

[0097] The analytical data of the product are as follows: optical rotation value: +29.78 (concentration 0.20, solvent is dichloromethane); HPLC (OD chiral column, isopropanol / n-hexane = 20 / 80, flow rate 1.0 mL / min, wavelength 254 nm), peak time 1 is 6.12 min, peak time 2 is 7.44 min, enantioselectivity is 60%. NMR characterization results: 1 H NMR (400MHz, CDCl3) δ8.08-7.92(m,2H),7.68-7.57(m,1H),7.49(t,J=7.7Hz,2H) ,7.44-7.28(m,5H),3.52(d,J=5.7Hz,1H),3.26-3.05(m,1H),2.76-2.55(m,1H). 13 C NMR (100MHz,CDCl3)δ195.8,138.4,135.9,133.9,128.9,128.6 128.4,127.9,126.2,44.1,43.6. High resolution characterization results are: HRMS (ESI) m / zcalcd for C 15 H 13 NO[M+Na] + =246.0890,found=246.0891.

[0098] It can be seen from the above experimental results that the ethyl- The base derivatives, due to the presence of a nitrogen chiral center, can effectively catalyze the aziridination reaction of chalcone, and the entire reaction conditions are mild, and the yield of the prepared product is moderate and the enantioselectivity of the product is moderate. Therefore, the compounds of the present invention are very suitable for use as chiral catalysts and can also provide a structural basis for the development of new catalysts.

[0099] In summary, the ethyl- Base derivatives, with nitrogen chiral centers and unique rigid structures, can provide a material structural basis for molecular recognition, supramolecular chemistry, asymmetric catalysis, and the discovery of new drug molecules, and are particularly suitable for use as chiral catalysts, providing a structural basis for the development of new catalysts. The above embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. An ethyl- Base derivatives, characterized in that The compound having the structure shown in formula I: In Formula I, Ar 1 ,Ar 2 is an aryl group containing a substituent; Among them, Ar 1 The substituent in is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy; Ar 2 The substituents are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, benzyl, hydrogen, fluorine, chlorine, bromine, methoxy, benzyloxy, and trimethylsilyl.

2. Ethyl- according to claim 1 Base derivatives, characterized in that The compounds Ⅰ-1 to Ⅰ-20 are as follows:

3. An ethyl- The method for preparing a base derivative is characterized in that: The following steps are involved: Compound 1, compound 2 and an inorganic base are mixed in an organic solvent, and then subjected to a bisallylation substitution reaction under the action of metal palladium and a chiral ligand to obtain an ethyl- Base class derivatives.

4. Ethyl- according to claim 3 The method for preparing a base derivative is characterized in that: The inorganic base is one of sodium carbonate, potassium carbonate and cesium carbonate; the organic solvent is one or more of chloroform, methane, dichloromethane and tetrahydrofuran.

5. Ethyl- The method for preparing a base derivative is characterized in that: In the compound 2, R is one of methyl, ethyl, tert-butyl and benzyl.

6. Ethyl- The method for preparing a base derivative is characterized in that: The metal palladium is Pd2(dba)3·CHCl3; the chiral ligand is N,N-bis((S)-1-phenylethyl)-4,5,6,7-tetrahydrobiindeno[7,1-de:1',7'-fg][1,3,2]dioxaphosphat-12-amine.

7. Ethyl- The method for preparing a base derivative is characterized in that: The temperature of the bisallyl substitution reaction is 50-70° C. and the time is 20-40 hours.

8. The ethyl- The method for preparing a base derivative is characterized in that: The molar ratio of the compound 1, the compound 2, the inorganic base, the metal palladium and the chiral ligand during the reaction is 1:(1.4-1.6):(1.8-2.2):(0.04-0.06):(0.14-0.16).

9. An ethyl- The application of base derivatives is characterized in that: Application of chiral catalyst in catalytic aziridine reaction.

10. Ethyl- The application of base derivatives is characterized in that: The aziridination reaction is an aziridination reaction of chalcone.

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