CN110229085A - Alcohol promotes imines and alkynes reductive coupling reaction to construct allylamine derivatives - Google Patents

Abstract

The present invention relates to one kind using alcohol as green and cheap reducing agent, and in the cheap transition metal-catalyzed lower intermolecular reductive coupling reaction for realizing common imines and common interior alkynes, for efficiently preparing polysubstituted allylamine derivatives, this method is economical and practical.The key that the present invention solves the problems, such as is: 1. find a kind of high rich electrical carbenes raising reactivity of big steric hindrance, while the chirality control of part substrate is realized by designing chiral carbenes；2. cheap metal nickel is used in combination with green reducing agent isopropanol, economical and practical and environmental-friendly, meet continuable development principle.

Description

Alcohol-promoted reductive coupling of imines and alkynes to construct allylamine derivatives

technical field

The invention relates to a synthesis method for generating allylamine derivatives from common internal alkynes and common imines, and belongs to the technical field of reductive coupling reactions.

Background technique

The allylamine structure not only exists in many pesticides and drug molecules, but also is an important intermediate in organic synthesis, especially drug synthesis. Therefore, how to construct multi-substituted allylamine structures cheaply and efficiently has high application and research value. Through this method, a series of three-substituted allylamine structures can be easily synthesized. The substituents on the alkenyl group can be either aryl or alkyl, and the aryl substituents are compatible with both the electron-donating group and the electro-absorbing group. ; The group connected to the α position of the alkenyl group can be either an aryl group or an alkyl group, and the aryl substituent can be either an electric-absorbing group or a donating group, and the adjacent and para-positions are compatible; With carbene ligands, we can realize the chiral regulation of some substrates, so it is of great significance to the study of drug synthesis.

Currently, multi-substituted allylamine derivatives can be synthesized by the following methods:

1) Alkenyl metal reagents are generated in situ from alkenyl halides or alkynes, and then alkenyl metal reagents react with imines to generate allylamine derivatives, or catalyzed by noble metal rhodium, alkenyl boron substrates react with imines , to obtain allylamine derivatives: this kind of method requires metal reagents that are extremely sensitive to air or water, requires anhydrous and oxygen-free conditions, and the operation is complicated, or alkenyl metal reagents need to be synthesized in advance, and noble metal catalysts are required. The reaction system Substrate functional group compatibility is poor. (Brak, K.; J.A. Ellman, J.A.J. Am. Chem. Soc. 2009, 131, 3850)

2) Allylamine derivatives can be obtained by direct reductive coupling of cheap and easy-to-obtain imines and alkynes. When the catalyst is cheap metal Ni, the reaction requires equivalent Et ₃ B, ZnEt ₂ , etc. as reducing agents, and clean When the reducing agent H2 is used, the reaction requires precious metal Rh as a catalyst: the system is very sensitive to water and oxygen. After the reaction of the metal reducing agent, an equivalent amount of organic waste will be produced, which will seriously pollute the environment; when hydrogen is used as the reducing agent, precious metals must be used. Rh is used as a catalyst, the reaction cost is high, and the reaction substrate of this system is limited. (Patel, SJ; Jamison, TF Angew. Chem., Int. Ed. 2003, 42, 1364; Zhou, CY; Zhu, SF; Wang, LX; Zhou, QLJ Am. Chem. Soc. 2010, 132, 10955; Ngai, MY.; Barchuk, A.; Krische, MJJ Am. Chem. Soc. 2007, 129, 12644)

In summary, although allylamine derivatives are of great significance in the synthesis of drugs, the existing synthetic methods are cumbersome and require strict operations, and the use of equivalent metal reagents increases the cost of preparation and causes serious environmental pollution. Expensive, high production cost, unable to mass-produce.

Contents of the invention

The purpose of the present invention is to provide an economical and practical method, which can use alcohol as a green and cheap reducing agent combined with cheap metal catalysis to realize the reductive coupling reaction of common imines and alkynes to prepare allylamine derivatives.

1. The preparation method of efficiently synthesizing allylamine derivatives is characterized in that the concrete steps of the method are:

In nitrogen atmosphere, add ligand (ligand), base (base), metal catalyst M _m X _n , solvent (solvent) and alcohol (alcohol) to the reaction flask in sequence, and finally add raw material 1 and raw material 2 at the specified temperature Stir for 18 hours, cool to room temperature, filter through celite, concentrate, and separate by column chromatography to obtain the target product.

2. The metal catalyst involved in the present invention is Ni(cod) ₂ .

3. The nitrogen heterocyclic carbene ligand involved in the present invention can be an alkyl-substituted carbene ligand, such as cyclohexyl, methyl, tert-butyl, etc., or an aryl-substituted carbene ligand, such as 2 , 6-diisopropylphenyl substituted or 2,4,6-trimethylphenyl substituted, can be a benzoquinone skeleton electron-withdrawing carbene ligand, or an acenaphthoquinone skeleton electron-donating carbene ligand; It can be a chiral carbene ligand, and the chiral source can be a chiral alkylamine or a chiral aniline.

When the chiral carbene ligand is the acenaphthoquinone skeleton and the chiral source is chiral aniline, the para-position R substituent of the chiral aniline can be methyl or tert-butyl; the aniline side chain aryl substituent can be phenyl or May be 3,5-dimethyl-substituted phenyl.

4. The alkali used in the present invention is potassium tert-butoxide, etc., but not limited thereto.

5. The alcohol involved in the present invention can be primary alcohols such as methanol, ethanol, n-propanol, benzyl alcohol, or isopropanol, 1-phenylethanol, 2,4-dimethyl-3-pentanol, Secondary alcohols such as 2-methylcyclohexanol, but not limited to these.

6. The solvent used in the present invention can be tetrahydrofuran, benzene, toluene, xylene, mesitylene, trifluorotoluene, DMF, ethyl acetate, etc., tetrahydrofuran is optimal, and the corresponding application amount is 5-10 mL per millimole of raw material 1.

7. The reaction temperature involved in the present invention can be in the range of 60°C to 140°C, 100°C is optimal for some products, and 60°C is optimal for chiral products.

8. The raw material 1 used in the present invention can be a symmetrical alkyl alkyne or a symmetrical aryl alkyne, and the aryl substituent can be at the aryl ortho, meta, or para position, and the substituent can be methyl, acetylene Donating groups such as radicals and methoxy groups may also be electron-withdrawing groups such as fluorine or trifluoromethyl; it may also be an asymmetric alkylaryl alkyne, or an asymmetric alkyl alkyne.

9. ^The R substituent in the raw material 2 used in the present invention can be p-methylphenyl or tert-butyl, the ^R substituent can be aryl or alkyl, and the alkyl can be cyclohexyl or tert-butyl etc., but not limited to these; the aryl group can be phenyl, naphthyl and thiophene substituents, wherein the substituents on the aryl group can be in the ortho, meta, para position, and can be methyl, methoxy, N , N-dimethyl group, etc., may also be electro-absorbing fluorine, trifluoromethyl group, etc., but not limited to these groups.

10. The R substituent in the product ³ of the present invention can be p-methylphenyl or tert ^- butyl, the ^R substituent can be ^an alkyl or aryl substituent, R and R can be the same, can be the same It can be an aryl group or both can be an alkyl group, R ¹ and R ² can also be different, can be an aryl group and an alkyl group, or can be different alkyl groups, and the above are not limited to these groups.

The advantages of the present invention are:

1. Most of the reagents used in the present invention are obtained commercially. The raw materials of the ligands to be synthesized have a wide range of sources, are cheap, and can exist stably at normal temperature and pressure. The operation is convenient and no special treatment is required.

2. The invention is easy to operate, and the target product can be obtained in one step reaction, and the cheap and easy-to-obtain alcohol is used as the reducing agent, which avoids the pre-preparation of sensitive alkenyl metal reagents by traditional methods; The use of dangerous reagents such as zinc-based reagents or alkyl boron reagents and silicon hydrogen reagents requires simple equipment, facilitates subsequent processing procedures, greatly reduces the production cost of synthesizing such compounds, and reduces environmental pollution.

3. The present invention uses cheap metals as catalysts, avoiding the use of precious metal rhodium, iridium or ruthenium reagents.

4. The present invention adopts a chiral all-carbon skeleton nitrogen-heterocyclic carbene ligand that is stable to both air and water, and can obtain optically pure allylamine derivatives in one step.

5. The reaction by-products of the present invention can be recycled, no waste by-products are generated, and meet the requirements of green chemistry.

Specific implementation method

The following implementation examples will better illustrate the present invention, but it should be emphasized that the present invention is by no means limited to the contents represented by these several implementation examples. The following examples show different aspects of the invention. Data presented include specific operating and reaction conditions and products. The purity of the product was identified by NMR. The chirality of the product was detected by chiral high performance liquid chromatography.

Example 1: Synthesis of (E)-4-Methyl-N-(1,2,3-triphenylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite, concentration and column chromatography, the target product 3a was obtained as a white solid in a yield (81%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.29-7.24(m, 5H), 7.24-7.17(m, 3H), 7.13(t, J=7.6Hz, 2H), 7.09-6.99(m, 3H), 6.78-6.72(m, 2H), 6.8(d, J=6.8Hz, 2H), 6.48(s, 1H), 5.36(d, J=7.6Hz, 1H ), 4.83(d, J=7.6Hz, 1H), 2.36(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.5, 139.8, 139.2, 137.7, 137.3, 136.0, 130.1, 129.6, 129.5, 129.3, 128.8, 128.7, 128.0, 127.9, 127.9, 127.5, 127.4, 127.2, 64.4, 21.6. HRMS (ESI) calcd. for C ₂₈ H ₂₉ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 457.1944, Found 457.1942.

Example 2: Synthesis of (E)-2-Methyl-N-(1,2,3-triphenylallyl)propane-2-sulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2b (54mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 3b was separated by column chromatography as a white solid in a yield of (65%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.43-7.33(m, 4H), 7.32-7.27(m, 1H), 7.26-7.19(m, 3H), 7.15-7.06(m, 3H), 6.98-6.91 (m, 2H), 6.89(d, J=6.8Hz, 2H), 6.78(s, 1H), 5.52(d, J=10.0Hz, 1H), 4.29(d, J=9.6Hz, 1H), 1.37 (s, 9H). ¹³ C NMR (100MHz, CDCl ₃ ) δ141.7, 140.2, 137.4, 136.1, 129.7, 129.6, 129.4, 128.9, 128.8, 128.1, 128.0, 127.8, 127.3, 127.1, 65.5, 60.3, 24.3 .HRMS(ESI)calcd.for C ₂₅ H ₃₁ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 423.2101, Found 423.2101.

Example 3: Synthesis of (E)-N-(2,3-diphenyl-1-(p-tolyl)allyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2c (65.5mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3c as a white solid in a yield (79%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.24-7.17(m, 3H), 7.17-7.10(m, 4H), 7.10-7.01(m, 5H), 6.79 -6.72(m, 2H), 6.69(d, J=6.8Hz, 2H), 6.48(s, 1H), 5.31(d, J=8.0Hz, 1H), 4.77(d, J=8.0Hz, 1H) , 2.36(s, 3H), 2.32(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.4, 139.9, 137.7, 137.6, 137.5, 136.2, 136.1, 129.8, 129.6, 129.4, 129.4, 129.3, 128.8, 127.9, 127.8, 127.5, 127.3, 127.1, 64.2, 21.6, 21.2. HRMS (ESI) calcd. for C ₂₉ H ₃₁ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 471.2101, Found 471.2100.

Example 4: Synthesis of (E)-N-(1-(4-Methoxyphenyl)-2,3-diphenylallyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2d (69.4mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3d as a white solid in a yield (82%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.23-7.11(m, 7H), 7.08-7.01(m, 3H), 6.80(d, J=8.8Hz, 2H ), 6.77-6.72(m, 2H), 6.70(d, J=6.8Hz, 2H), 6.47(s, 1H), 5.30(d, J=7.6Hz, 1H), 4.76(d, J=7.6Hz , 1H), 3.79(s, 3H), 2.36(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ159.3, 143.5, 140.0, 140.0, 137.8, 137.5, 136.0, 131.2, 129.6, 129.4, 129.3 , 128.8, 128.6, _128.0 , _127.8 , _127.5 , _127.1 , _114.0 , 63.9 ^, 55.4, 21.6.

Example 5: Synthesis of (E)-N-(1-(3-Methoxyphenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2e (69.4mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3e as a white solid in a yield of (77%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.69 (d, J=8.0Hz, 2H), 7.24-7.18 (m, 4H), 7.17-7.10 (m, 2H), 7.09-7.00 (m, 3H), 6.88 (d, J=7.6Hz, 1H), 6.82-6.73(m, 4H), 6.70(d, J=7.2Hz, 2H), 6.48(s, 1H), 5.32(d, J=8.0Hz, 1H) , 4.79(d, J=8.0Hz, 1H), 3.72(s, 3H), 2.36(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ159.9, 143.5, 140.8, 139.7, 137.7, 137.3, 136.0, 130.1, 129.7, 129.6, 129.5, 129.3, 128.8, 128.0, 127.9, 127.5, 127.2, 119.7, 113.4, 112.9, 64.4, 55.3, 21.6.HRMS(ESI)calcd.for C ₂₉ H ₃₁ N ₂ O ₃ S ([M+NH ₄ ] ⁺ ) 487.2050, Founnd 487.2046.

Example 6: Synthesis of (E)-N-(1-(2-Methoxyphenyl)-2,3-diphenylallyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, ligands AnIPrHCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF (1.0 mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2f (69.4mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, diluted with ethyl acetate, silicon After filtration with alginate, concentration and separation by column chromatography, the target product 3f was obtained as a white solid in a yield of (68%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.55(d, J=8.0Hz, 2H), 7.23-7.10(m, 4H), 7.08-6.99(m, 5H), 6.96(d, J=7.6Hz, 1H ), 6.87(d, J=7.2Hz, 2H), 6.79-6.72(m, 3H), 6.70(d, J=8.0Hz, 1H), 6.48(s, 1H), 5.47(s, 2H), 3.66 (s, 3H), 2.29(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ156.7, 142.9, 140.4, 138.7, 137.7, 136.5, 129.3, 129.2, 128.9, 128.5, 128.4, 127.8, 127.3, 127.1, 126.8, 126.8, 120.5, 110.9, 61.1, 55.4, 21.5. HRMS (ESI) calcd. for C ₂₉ H ₃₁ N ₂ O ₃ S ([M+NH ₄ ] ⁺ ) 487.2050, Found 487.2047.

Example 7: Synthesis of (E)-N-(1-(2,4-Dimethoxyphenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw material 1a (35.6mg, 0.2mmol) and 2g (77mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, Filtrate with celite, concentrate and separate by column chromatography to obtain 3 g of the target product as a white solid in a yield (87%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.56(d, J=8.4Hz, 2H), 7.23-7.12(m, 3H), 7.07(d, J=8.0Hz, 2H), 7.05-6.98(m, 3H), 6.93-6.83(m, 3H), 6.80-6.69(m, 2H), 6.48(s, 1H), 6.31-6.24(m, 2H), 5.41(d, J=8.4Hz, 1H), 5.36 (d, J=8.4Hz, 1H), 3.75(s, 3H), 3.62(s, 3H), 2.30(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ 160.5, 157.7, 142.8, 140.6, _{138.8,137.8,136.5,129.9,129.3,129.2,128.5,128.2,127.8,127.2,127.1,126.7,119.4,104.0,98.8,60.6,55.4,55.4,21.5 . 4} S ([M+Na] ⁺ )522.1710, Found 522.1700.

Example 8: Synthesis of (E)-N-(2,3-Diphenyl-1-(3,4,5-trimethoxyphenyl)allyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2h (84mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite, after concentration, the target product 3h was separated by column chromatography as a white solid in a yield (89%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.0Hz, 2H), 7.24-7.20(m, 3H), 7.17(t, J=7.4Hz, 2H), 7.11-7.02(m, 3H), 6, 80-6.70(m, 4H), 6.48(s, 1H), 6.43(s, 2H), 5.29(d, J=7.6Hz, 1H), 4.85(d, J=7.6Hz, 1H ), 3.82(s, 3H), 3.72(s, 6H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ153.2, 143.5, 139.8, 137.8, 137.4, 137.3, 136.0, 134.7, 129.8, 129.5, 129.5, 129.3, 128.8, 128.0, 127.9, 127.4, 127.2, 104.5, 64.5, 60.9, 56.1, 21.5. HRMS (ESI) calcd. for C ₃₁ H ₃₅ N ₂ O ₅ S ([M+NH ₄ ] ⁺ )547.2261, Found 547.2257.

Embodiment 9:

Synthesis of (E)-N-(1-(4-(Dimethylamino)phenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2i (72.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3i as a white solid in a yield (87%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.71(d, J=8.0Hz, 2H), 7.20(d, J=8.4Hz, 2H), 7.18-7.11(m, 3H), 7.09(d, J=8.4 Hz, 2H), 7.07-7.01(m, 3H), 6.81-6.69(m, 4H), 6.61(d, J=8.4Hz, 2H), 6.51(s, 1H), 5.24(d, J=7.2 Hz , 1H), 4.72(d, J=7.2Hz, 1H), 2.93(s, 6H), 2.35(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ150.2, 143.2, 140.3, 138.1, 138.0 , 136.3, 129.6, 129.5, 129.3, 129.1, 128.6, 128.4, 127.9, 127.6, 127.5, 126.9, 126.5, 112.5, 64.0, 40.6, 21.6.HRMS(ESI)calcd.for C ₃₀ H ₃₁ N ₂ O ₂ S( [M+H] ⁺ )483.2101, Found 483.2100.

Example 10: Synthesis of (E)-N-(1-(4-Fluorophenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2j (66.5mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3j as a white solid in a yield of (74%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.67 (d, J=8.4Hz, 2H), 7.24-7.18 (m, 5H), 7.18-7.12 (m, 2H), 7.10-7.01 (m, 3H), 6.95 (t, J=8.6Hz, 2H), 6.77-6.71(m, 2H), 6.68(d, J=7.2Hz, 2H), 6.45(s, 1H), 5.34(d, J=8.0Hz, 1H) , 4.90(d, J=8.0Hz, 1H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ162.3(d, J=245.1Hz), 143.6, 139.7, 137.6, 137.2, 135.8 , 135.0 (d, J=3.0Hz), 130.1, 129.6, 129.4, 129.3, 129.1 (d, J=8.0Hz), 128.9, 128.0, 128.0, 127.4, 127.3, 115.5 (d, J=21.4Hz), 63.8 , 21.6. ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-114.9. HRMS (ESI) calcd. for C ₂₈ H ₂₈ FN ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 475.1850, Found 475.1858.

Example 11: Synthesis of (E)-N-(1-(4-Fluorophenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2k (66.5mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3k as a white solid, the yield (64%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.4Hz, 2H), 7.26-7.19(m, 4H), 7.15(t, J=7.4Hz, 2H), 7.12-7.02(m, 4H ), 7.02-6.91(m, 2H), 6.75(d, J=8.0Hz, 2H), 6.67(d, J=7.2Hz, 2H), 6.45(s, 1H), 5.35(d, J=8.0Hz , 1H), 4.86(d, J=8.0Hz, 1H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ163.0(d, J=245.0 Hz), 143.7, 142.1, 142.0, 139.3, 137.6, 136.8, 135.7, 130.7, 130.2 (d, J = 8.2Hz), 129.7, 129.4 (d, J = 5.8Hz), 129.0, 128.1, 128.0, 127.5, 127.4, 123.0 (d, J = 2.6Hz ), 114.8 (d, J=21.1Hz), 114.4 (d, J=22.5Hz), 64.0, ^21.6.19 F NMR (376MHz, CDCl ₃ ) δ-111.9.HRMS (ESI) calcd.for C ₂₈ H ₂₈ FN ₂ O ₂ S([M+NH ₄ ] ⁺ )475.1850, Found475.1856.

Example 12: Synthesis of (E)-N-(1-(2-Fluorophenyl)-2,3-diphenylallyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), and finally added raw materials 1a (35.6mg, 0.2mmol) and 21 (66.5mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 31 as a white solid in a yield (64%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.58(d, J=7.6Hz, 2H), 7.24-7.12(m, 5H), 7.11(d, J=7.6Hz, 2H), 7.07-6.97(m, 4H), 6.92(t, J=9.4Hz, 1H), 6.87-6.80(m, 2H), 6.78-6.69(m, 2H), 6.42(s, 1H), 5.55(d, J=7.6Hz, 1H ), 5.04(d, J=7.6Hz, 1H), 2.33(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ160.2(d, J=245.7Hz), 143.3, 139.4, 137.6, 137.1, 135.9, 129.7, 129.5, 129.5, 129.3, 129.2(d, J=3.6Hz), 128.8, 127.9, 127.8, 127.2, 126.7, 126.6, 124.1(d, J=3.4Hz), 115.6(d, J=21.4Hz ), _59.0 , _21.6 . ¹⁹ F NMR (376 MHz, CDCl ₃ ) ^δ _{- 116.7 .}

Example 13:

Synthesis of (E)-N-(2,3-Diphenyl-1-(4-(trifluoromethyl)phenyl)allyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35, 6mg, 0.2mmol) and 2m (78.5mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate Diluted, filtered with celite, concentrated and separated by column chromatography to obtain the target product 3m as a white solid in a yield (29%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.63(d, J=8.4Hz, 2H), 7.51(d, J=8.4Hz, 2H), 7.40(d, J=8.4Hz, 2H), 7.25-7.13( m, 5H), 7.11-7.00(m, 3H), 6.74(d, J=7.6Hz, 2H), 6.66(d, J=7.2Hz, 2H), 6.44(s, 1H), 5.41(d, J = 8.0Hz, 1H), 4.92(d, J=8.0Hz, 1H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.7, 143.3, 139.2, 137.3, 136.8, 135.6, 130.7 , 129.9(q, J=32.4Hz), 129.7, 129.3, 129.0, 128.1, 128.0, 127.8, 127.5, 127.4, 125.5(q, J=3.6Hz), 124.1(q, J=270.5Hz), 64.1, 21.5 . ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-62.3. HRMS (ESI) calcd. for C ₂₉ H ₂₈ F ₃ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 525.1818, Found 525.1820.

Example 14: Synthesis of (E)-4-Methyl-N-(1-(naphthalen-1-yl)-2,3-diphenylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2n (74.2mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3n as a white solid with a yield of (65%). ¹ HNMR (400MHz, CDCl ₃ ) δ8.15-8.05(m, 1H), 7.88-7.80(m, 1H), 7.76(d, J=8.0Hz, 1H), 7.63(d, J=8.0Hz, 2H ), 7.56-7.43(m, 3H), 7.35(t, J=7.6Hz, 1H), 7.21-7.11(m, 3H), 7.08(d, J=8.0Hz, 2H), 7.06-6.98 (m, 3H), 6.96(d, J=6.8Hz, 2H), 6.69(d, J=6.8Hz, 2H), 6.44(s, 1H), 6.14(d, J=6.4Hz, 1H), 4.98(d, J=6.4Hz, 1H), 2.28(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.3, 139.1, 138.5, 137.7, 136.1, 134.1, 134.1, 131.1, 130.5, 129.5, 129.3, 129.1, 129.0, 128.9, 128.8, 127.9, 127.7, 127.3, 127.1, 126.8, 126.2, 125.9, 125.2, 123.3, 60.7, 21.5. HRMS (ESI) calcd. for C ₃₂ H ₃₁ N ₂ O ₂ S ([M+NH ₄ ] ⁺ )507.2101, Found 507.2094.

Example 15: Synthesis of (E)-4-Methyl-N-(1-(naphthalen-2-yl)-2,3-diphenylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2o (74.2mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3o as a white solid with a yield of (78%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.85-7.79(m, 1H), 7.77(d, J=8.8Hz, 1H), 7.74-7.64(m, 4H), 7.52-7.44(m, 2H), 7.42 (d, J=8.4Hz, 1H), 7.22-7.14(m, 3H), 7.14-7.02(m, 5H), 6.77(d, J=6.8Hz, 2H), 6.69(d, J=7.6Hz, 2H), 6.55(s, 1H), 5.52(d, J=8.0Hz, 1H), 4.91(d, J=8.0Hz, 1H), 2.32(s, 3H). ¹³ C NMR (100 MHz, CDCl ₃ )δ143.4, 139.7, 137.6, 137.4, 136.4, 135.9, 133.2, 132.8, 130.2, 129.5, 129, 4, 129.3, 128.8, 128.5, 128.2, 127.9, 127.8, 127.6, 127.4, 1267.2, 126 , 125.2, 64.5, 21.5. HRMS (ESI) calcd. for C ₃₂ H ₃₁ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 507.2101, Found 507.2099.

Example 16: Synthesis of (E)-N-(2,3-Diphenyl-1-(thiophen-2-yl)allyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2p (63.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3p as a white solid, the yield (65%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.73(d, J=8.0Hz, 2H), 7.25-7.20(m, 4H), 7.16(t, J=7.4Hz, 2H), 7.12-7.03(m, 3H ), 6.97-6.89(m, 2H), 6.84-6.78(m, 2H), 6.76(d, J=6.8Hz, 2H), 6.56(s, 1H), 5.59(d, J=8.4Hz, 1H) , 4.89 (d, J=8.4Hz, 1H), 2.37 (s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ144.4, 143.7, 139.6, 137.7, 136.7, 135.8, 130.0, 129.7, 129.5, 129.4 , 128.9, 128.1, 128.0, 127.5, 127.4, 127.3, 125.9, 125.8, 60.8, 21.6. HRMS (ESI) calcd. for C ₂₆ H ₂₇ N ₂ O ₂ S ₂ ([M+NH ₄ ] ⁺ )463.1508, Found 463.1507.

Example 17: Synthesis of (E)-N-(1-Cyclohexyl-2,3-diphenylallyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2q (63.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3q as a white solid in a yield (83%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.77(d, J=8.4Hz, 2H), 7.30-7.24(m, 3H), 7.21(d, J=8.0Hz, 2H), 7.09-6.96(m, 3H ), 6.88-6.78(m, 2H), 6.68-6.59(m, 2H), 6.19(s, 1H), 4.43(d, J=9.6Hz, 1H), 3.92(t, J=9.0Hz, 1H) , 2.30(s, 3H), 1.96(d, J=12.4Hz, 1H), 1.86-1.68(m, 3H), 1.64(s, 1H), 1.43-1.29(m, 1H), 1.24-1.02(m , 4H), 1.01-0.84 (m, 1H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.3, 138.8, 138.4, 137.7, 136.1, 130.1, 129.6, 129.4, 129.1, 128.9, 127.8, 127.7, 127.4, 126.8, 66.8, 40.1, 31.0, 28.9, 26.4, 26.1, 21.5. HRMS (ESI) calcd. for C ₂₈ H ₃₅ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 463.2414, Found 463.2410.

Example 18: Synthesis of (E)-N-(4,4-Dimethyl-1,2-diphenylpent-1-en-3-yl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (42.8mg, 0.24mmol) and 2r (47.9mg, 0.2mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3r as a white solid, the yield (23%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.79(d, J=8.0Hz, 2H), 7.23-7.15(m, 3H), 7.09(d, J=8.0Hz, 2H), 7.06-6.96(m, 5H ), 6.62-6.52(m, 2H), 6.24(s, 1H), 5.00(d, J=9.2Hz, 1H), 4.10(d, J=9.2Hz, 1H), 2.18(s, 3H), 0.84 (s, 9H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.2, 140.0, 139.1, 138.2, 136.6, 131.5, 129.8, 129.6, 129.2, 128.6, 127.7, 127.4, 126.6, 68.8, 36.5, 27.3, 21.4 .HRMS(ESI)calcd.for C ₂₆ H ₂₉ NNaO ₂ S ([M+Na] ⁺ ) 442.1811, Found 442.1815.

Example 19: Synthesis of (E)-4-Methyl-N-(1-phenyl-2,3-di-p-tolylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1b (41.3mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 4a was separated by column chromatography as a white solid in a yield (81%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.4Hz, 2H), 7.33-7.26(m, 5H), 7.20(d, J=8.0Hz, 2H), 6.94(d, J= 8.0Hz, 2H), 6.87(d, J=8.0Hz, 2H), 6.66(d, J=8.0Hz, 2H), 6.54(d, J=8.0Hz, 2H), 6.38(s, 1H), 5.33 (d, J=8.0Hz, 1H), 4.83(d, J=8.0Hz, 1H), 2.37(s, 3H), 2.28(s, 3H), 2.22(s, 3H). ¹³ C NMR (100 MHz , CDCl ₃ ) δ143.4, 139.5, 138.8, 137.8, 137.5, 136.9, 134.2, 133.2, 129.9, 129.5, 129.5, 129.3, 129.2, 128.7, 128.6, 127.7, 127.5, 127.4, 12.5, 21.6 HRMS (ESI) calcd. for C ₃₀ H ₃₃ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 485.2257, Found 485.2253.

Example 20: Synthesis of (E)-4-Methyl-N-(1-phenyl-2,3-di-m-tolylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1c (41.3mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 4b was separated by column chromatography as a white solid in a yield of (77%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.0Hz, 2H), 7.33-7.26(m, 5H), 7.21(d, J=8.0Hz, 2H), 7.04-6.97(m, 2H), 6.95-6.84(m, 2H), 6.60(s, 1H), 6.52(d, J=7.2Hz, 1H), 6.48-6.41(m, 2H), 6.40(s, 1H), 5.34(d , J = 7.6Hz, 1H), 4.81 (d, J = 7.6Hz, 1H), 2.37 (s, 3H), 2.14 (s, 6H). ¹³ CNMR (100MHz, CDCl ₃ ) δ 143.3, 139.8, 139.4, 138.3, 137.8, 137.3, 137.2, 135.9, 130.3, 130.0, 129.9, 129.6, 128.6, 128.5, 128.5, 127.9, 127.8, 127.7, 127.4, 127.4, 126.5, 126.2, 64.5, 21.6, 2 HR calcd. for C ₃₀ H ₃₃ N ₂ O ₂ S([M+NH ₄ ] ⁺ )485.2257, Found 485.2255.

Example 21: Synthesis of (E/Z)-4-Methyl-N-(1-phenyl-2,3-di-o-tolylallyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1d (41.3mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite, concentration and column chromatography, the target product 4c was obtained as a white solid in a yield of (64%, Z/E=1:1). ¹ H NMR (400 MHz, CDCl ₃ ) δ7.62(d, J=8.4Hz, 2H), 7.60(d, J=8.0Hz, 2H), 7.25-7.17(m, 8H), 7.17-7.11(m , 4H), 7.10-7.00(m, 7H), 6.99-6.80(m, 7H), 6.75-6.65(m, 3H), 6.62(d, J=7.6Hz, 1H), 6.49(d, J=7.6 Hz, 1H), 6.43(d, J=7.6Hz, 1H), 5.33(d, J=6.8Hz, 1H), 5.10(d, J=6.0Hz, 1H), 5.07-4.98 (m, 2H), 2.37(s, 3H), 2.33(s, 3H), 2.28(s, 3H), 2.20(s, 3H), 1.78(s, 3H), 1.55(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ )δ 143.3, 143.2, 140.2, 139.7, 139.3, 139.2, 137.5, 137.3, 136.9, 136.7, 136.4, 136.4, 136.3, 136.2, 135.5, 135.4, 130.5, 130.3, 135.0, 2.8, 149.7, 28 , 128.3, 128.3, 128.1, 127.8, 127.6, 127.6, 127.3, 127.3, 127.2, 127.2, 127.0, 125.7, 125.4, 125.1, 64.3, 64.3, 21.5, 21.5, 20.0, 19.9, 19.3 .for C ₃₀ H ₃₃ N ₂ O ₂ S([M+NH ₄ ] ⁺ )485.2257, Found485.2252.

Example 22: Synthesis of (E)-N-(2,3-bis(4-ethylphenyl)-1-phenylallyl)-4-methylbenzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1e (47mg, 0, 2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 4d as a white solid in a yield (72%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.35-7.24(m, 5H), 7.21(d, J=8.0Hz, 2H), 6.97(d, J= 8.0Hz, 2H), 6.89(d, J=8.0Hz, 2H), 6.67(d, J=8.0Hz, 2H), 6.56(d, J=8.0Hz, 2H), 6.37(s, 1H), 5.33 (d, J=8.0Hz, 1H), 4.79(d, J=8.0Hz, 1H), 2.59(q, J=7.6Hz, 2H), 2.52(q, J=7.6Hz, 2H), 2.37(s , 3H), 1.20(t, J=7.6Hz, 3H), 1.14(t, J=7.6Hz, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.8, 143.4, 143.3, 139.6, 138.7, 137.8 , 134.4, 133.4, 130.0, 129.6, 129.3, 129.3, 128.6, 128.3, 127.7, 127.5, 127.4, 64.6, 28.6, 28.6, 21.6, 15.4, 15.3. HRMS (ESI) calcd. for C ₃₂ H ₃₇ N ₂ O ₂ S([M+NH ₄ ] ⁺ ) 513.2570, Found 513.2564.

Example 23: Synthesis of (E)-N-(2,3-bis(4-methoxyphenyl)-1-phenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1f (47.7mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 4e was separated by column chromatography as a white solid in a yield (74%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.0Hz, 2H), 7.31-7.23(m, 5H), 7.20(d, J=8,0Hz, 2H), 6.73-6.64(m , 4H), 6.63-6.54(m, 4H), 6.35(s, 1H), 5.31(d, J=8.0Hz, 1H), 4.82(d, J=8.0Hz, 1H), 3.76(s, 3H) , 3.72(s, 3H), 2.37(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ159.1, 158.7, 143.4, 139.6, 137.8, 137.4, 137.3, 130.7, 130.6, 129.6, 129.3, 128.7, 128.6, 127.7, 127.5, 127.3, 114.3, 113.4, 64.6, 55.3, 21.6. HRMS (ESI) calcd. for C ₃₀ H ₂₉ NNaO ₄ S ([M+Na] ⁺ ) 522.1710, Found 522.1713.

Example 24: Synthesis of (E)-N-(2,3-bis(4-fluorophenyl)-1-phenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1g (42.8mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 4f was separated by column chromatography as a white solid in a yield of (73%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=7.2Hz, 2H), 7.33-7.15(m, 8H), 6.85(t, J=8.0Hz, 2H), 6.80-6.63(m, 5H), 6.52(s, 1H), 5.31(d, J=8.0Hz, 1H), 4.80(d, J=8.0Hz, 1H), 2.37(s, 3H). ¹³ CNMR(100MHz, CDCl ₃ )δ162 .3(d, J=246.0Hz), 161.8(d, J=246.2Hz), 143.6, 139.0, 138.8, 137.7, 133.2(d, J=3.3Hz), 131.9(d, J=3.3Hz), 131.2 (d, J=7.8Hz), 130.9(d, J=7.8Hz), 129.6, 129.0, 128.8, 128.0, 127.4, 127.3, 115.9(d, J=21.3Hz), 115.0(d, J=21.1Hz) , 64.4, 21.6. ¹⁹ F NMR (376MHz, CDCl ₃ ) δ-113.4, -114.0. HRMS (ESI) calcd.for C ₂₈ H ₂₇ F ₂ N ₂ O ₂ S ([M+NH ₄ ] ⁺ ) 493.1756, Found 493.1752.

Example 25:

Synthesis of (E)-4-Methyl-N-(1-phenyl-2,3-bis(4-(trifluoromethyl)phenyl)allyl)benzenesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1h (62.8mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, Filtrate with celite, concentrate and separate by column chromatography to obtain 4 g of the target product as a white solid, the yield (53%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.0Hz, 2H), 7.42(d, J=8.0Hz, 2H), 7.33(d, J=8.0Hz, 2H), 7.30-7.26 (m, 3H), 7.20(d, J=8.0Hz, 2H), 7.18-7.13(m, 2H), 6.89(d, J=8.0Hz, 2H), 6.85(d, J=8.0Hz, 2H) , 6.71(s, 1H), 5.32(d, J=6.8Hz, 1H), 4.89(d, J=6.8Hz, 1H), 2.36(s, 3H). ¹³ C NMR(100MHz, CDCl ₃ )δ143. ( q, J=3.6Hz), 125.0(q, J=3.6Hz), 124.0(q, J=270.6Hz), 124.1(q, J=270.3Hz), 64.1, 21.5.HRMS(ESI)calcd.for C ₃₀ H ₂₇ F ₆ N ₂ O ₂ S ([M+NH ₄ ] ⁺ )593.1692, Found 593.1691.

Example 26: Synthesis of (E)-4-Methyl-N-(1-phenyl-2-propylhex-2-en-1-yl)benzenesulfonamide

In a nitrogen atmosphere, ligands AnIPrHCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF (1.0 mL), i-PrOH (1.0mL), finally added raw materials li (22mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, diatomaceous earth After filtration, concentration and separation by column chromatography, the target product 4h was obtained as a white solid in a yield (52%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.62(d, J=8.4Hz, 2H), 7.23-7.16(m, 5H), 7.12-7.06(m, 2H), 5.24(t, J=7.2Hz, 1H), 4.88(d, J=7.6Hz, 1H), 4.72(d, J=7.6Hz, 1H), 2.39(s, 3H), 1.97-1.84(m, 3H), 1.76-1.64(m, 1H ), 1.25(q, J=7.2Hz, 2H), 1.20(q, J=7.2Hz, 2H), 0.83(t, J=7.2Hz, 3H), 0.78(t, J=7.2Hz, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ143.0, 140.0, 137.9, 137.9, 129.4, 128.9, 128.4, 127.4, 127.4, 127.3, 62.0, 31.0, 29.8, 22.8, 22.1, 21.5, 14.3, 14.0. HRMS (ESI )calcd.for C ₂₂ H ₂₉ NNaO ₂ S([M+Na] ⁺ ) 394.1811, Found 394.1815.

Example 27:

Synthesis of (E)-N-(1-(4-(dimethylamino)phenyl)-2-propylhex-2-en-1-yl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials li (22mg, 0.2mmol) and 2i (72.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute, After filtration with celite and concentration, the target product 4i was separated by column chromatography as a white solid in a yield (78%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.63(d, J=8.4Hz, 2H), 7.20(d, J=8.4Hz, 2H), 6.91(d, J=8.8Hz, 2H), 6.55(d , J=8.8Hz, 2H), 5.33(t, J=7.0Hz, 1H), 4.77(d, J=6.8Hz, 1H), 4.64(d, J=6.8Hz, 1H), 2.90(s, 6H ), 2.39(s, 3H), 2.00-1.83(m, 3H), 1.70-1.56(m, 1H), 1.34-1.13(m, 4H), 0.85(t, J=7.2Hz, 3H), 0.78 ( t, J=7.2Hz, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ150.0, 142.8, 138.1, 138.0, 129.3, 128.3, 127.7, 127.6, 127.4, 112.4, 61.5, 40.6, 31.2, 29.8, 22.9 , 22.0, 21.6, 14.3, 14.0. HRMS (ESI) calcd. for C ₂₄ H ₃₅ N ₂ O ₂ S ([M+H] ⁺ ) 415.2414, Found 415.2413.

Example 28:

Synthesis of (E)-N-(1-(4-(dimethylamino)phenyl)-2-methylbut-2-en-1-yl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1j (10.8mg, 0.2mmol) and 2i (72.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 4j as a white solid, the yield (55%). ¹ HNMR (400MHz, CDCl ₃ ) δ7.64(d, J=8.0Hz, 2H), 7.21(d, J=8.0Hz, 2H), 6.94(d, J=8.8Hz, 2H), 6.57(d, J=8.8Hz, 2H), 5.45(q, J=6.8Hz, 1H), 4.75(d, J=7.2Hz, 1H), 4.64(d, J=7.2Hz, 1H), 2.90(s, 6H) , 2.40(s, 3H), 1.49(d, J=6.8Hz, 3H), 1.33(s, 3H). ¹³ C NMR(100MHz, CDCl ₃ ) δ150.0, 142.9, 137.9, 134.0, 129.3, 127.8, _127.5 ^, _127.2 , _122.5 , _112.4 , 64.0, 40.6, 21.6, 13.3, 13.0.

Example 29:

(E)-N-(1-(4-(dimethylamino)phenyl)-2-methyl-3-phenylallyl)-4-methylbenzonesulfonamide and (E)-N-(1-(4-(dimethylamino)phenyl)-2 Synthesis of -phenylbut-2-en-1-yl)-4-methylbenzonesulfonamide(2.6∶1 mixture)

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 1k (23.2mg, 0.2mmol) and 2i (72.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 4k as a yellow oil with a yield (48%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.71(d, J=8.4Hz, 2H), 7.62(d, J=8.4Hz, 0.78H), 7.23-7.26(m, 1.95H), 7.24-7.15( m, 5H), 7.07(d, J=7.6Hz, 2H), 7.05(d, J=8.8Hz, 2H), 6.99(d, J=8.8Hz, 0.78H), 6.80-6.74(m, 0.78H ), 6.61(d, J=8.8Hz, 2H), 6.57(d, J=8.8Hz, 0.78H), 6.46(s, 1H), 5.66(q, J=6.6Hz 0.39H), 5.11 (d, J=7.2Hz, 0.39H), 4.94(d, J=7.2Hz, 1H), 4.81(d, J=7.2Hz, 1H), 4.63(d, J=7.2Hz, 0.39H), 2.92(s, 6H), 2.91(s, 2.34H), 2.41(s, 1.17H), 2.37(s, 3H), 1.58(s, 3H), 1.43(d, J=7.2Hz, 1.17H). ¹³ C NMR ( 100MHz, CDCl ₃ ) δ150.1, 150.0, 143.1, 142.9, 140.3, 138.0, 137.9, 137.4, 136.2, 129.5, 129.4, 129.3, 129.0, 128.2, 128.1, 128.0, 127.9, 127.6, 127.5 , 126.7, 126.5, 125.0, 112.5, 112.4, 64.4, 63.1, 40.6, 40.6, 21.6, 21.5, 15.2, 14.5. HRMS (ESI) calcd. for C ₂₅ H ₂₉ N ₂ O ₂ S ([M+H] ⁺ ) 421.1944, Found 421.1948.

Example 30:

(E)-N-(1-(4-(dimethylamino)phenyl)-2-ethylidenepentyl)-4-methylbenzonesulfonamide and (E)-N-(1-(4-(dimethylamino)phenyl)-2-methylhex-2 Synthesis of -en-1-yl)-4-methylbenzonesulfonamide(1.4∶1 mixture)

In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) ₂ (5.5mg, 10mol%), THF were sequentially added to the reaction flask (1.0mL), i-PrOH (1.0mL), finally added raw materials 11 (16.4mg, 0.2mmol) and 2i (72.6mg, 0.24mmol), stirred at 100°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 41, yellow oil, yield (49%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.66(d, J=8.0Hz, 1.42H), 7.62(d, J=8.0Hz, 2H), 7.21(d, J=7.2Hz, 1.42H), 7.19 (d, J=7.6Hz, 2H), 6.96(d, J=8.8Hz, 1.42H), 6.89(d, J=8.8Hz, 2H), 6.57(d, J=8.8Hz, 1.42H), 6.54 (d, J=8.8Hz, 2H), 5.40(q, J=6.8Hz, 1H), 5.36(t, J=6.8Hz, 0.71H), 4.79-4.71(m, 2.42H), 4.65(d, J=6.8Hz, 1H), 2.90(s, 4.26H), 2.90(s, 6H), 2.40(s, 2.13H), 2.39(s, 3H), 2.00-1.83(m, 2H), 1.74-1.62 (m, 1H), 1.52(d, J=6.4Hz, 3H), 1.35(s, 2.13H), 1.32-1.17(m, 3.84H), 0.85(t, J=7.2Hz, 2.13H), 0.79 (t, J=7.2Hz, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ149.9, 142.8, 142.7, 138.9, 138.0, 133.3, 129.9, 129.6, 129.5, 129.3, 129.2, 128.2, 128.0, 127.8, 127.6, 127.3, 126.4, 121.9, 112.4, 112.4, 63.9, 61.6, 40.6, 30.7, 29.8, 22.5, 21.6, 21.5, 14.2, 13.9, 13.3. HRMS (ESI) calcd. for C ₂₂ H ₃₁ N ₂ O ₂ S ([M+H] ⁺ )387.2101, Found 387.2090.

Example 31:

Synthesis of (S, E)-N-(1-(4-(Dimethylamino)phenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1a (17.8mg, 0.1mmol) and 2i (36.3mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 3i as a white solid, the yield (55%). HPLCcondition: Chiralpak AD-H column, n-hexane/i-PrOH=90:10, 1.0mL/min, 254nm, t _r-major =19.7min, t _r-minor =23.5min, 91%ee. (c 0.2, CHCl ₃ ).

Example 32:

Synthesis of (S, E)-N-(1-(4-(Diethylamino)phenyl)-2,3-diphenylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1a (17.8mg, 0.1mmol) and 2s (39.6mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 5a as a white solid in a yield (60%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.70(d, J=8.0Hz, 2H), 7.23-7.11(m, 5H), 7.09-7.02(m, 5H), 6.79(d, J=8.0Hz, 2H), 6.77-6.73(m, 2H), 6.54(d, J=8.8Hz, 2H), 6.51(s, 1H), 5.22(d, J=7.2Hz, 1H), 4.72(d, J=7.2 Hz, 1H), 3.32(q, J=7.2Hz, 4H), 2.35(s, 3H), 1.14(t, J=7.2Hz, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ147.4, 143.2 , 140.3, 138.2, 137.9, 136.4, 129.5, 129.4, 129.3, 128.9, 128.6, 128.6, 127.8, 127.5, 127.4, 126.8, _125.2 , 111.7, 63.9, 44.4, 21.5, 12.6. H ₃₅ N ₂ O ₂ S ([M+H] ⁺ ) 511.2414, Found 511.2417. HPLCcondition: Chiralpak AD-H column, n-hexane/i-PrOH=90:10, 1.0mL/min, 254nm, t _{r- major} =12.5min, t _r-minor =16.2min, 95%ee. (c 1.0, CHCl ₃ ).

Example 33: Synthesis of (S, E)-4-Methyl-N-(1-(4-morpholinophenyl)-2,3-diphenylallyl)benzenesulfonamide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1a (17.8mg, 0.1mmol) and 2t (39.6mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 5b as a white solid, the yield (35%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.23-7.10(m, 7H), 7.08-7.00(m, 3H), 6.81(d, J=8.0Hz, 2H), 6.78-6.68(m, 4H), 6.47(s, 1H), 5.28(d, J=7.6Hz, 1H), 4.81(d, J=7.6Hz, 1H), 3.86(t, J=4.4 Hz, 4H), 3.14(t, J=4.4Hz, 4H), 2.36(s, 3H). ¹³ C NMR (100MHz, CDCl ₃ ) δ150.7, 143.3, 140.0, 137.8, 137.7, 136.1, 130.3, 129.5 , 129.4, 129.4, 129.3, 128.7, 128.4, 127.9, 127.7, 127.4, 127.0, 115.5, 66.9, 63.9, 49.2, _21.6.HRMS (ESI) _{calcd.forC32H33N2O3S} ([ _{M +} H] ⁺ )525.2206, Found 525.2211.HPLC condition: Chiralpak AD-Hcolumn, n-hexane/i-PrOH=85:15, 1.0mL/min, 254 nm, t _r-major ＝23.3min, t _r-minor ＝46.1min , 51% ee. (c 0.5, CHCl ₃ ).

Example 34:

Synthesis of (S, E)-N-(1-(4-(Diethylamino)phenyl)-2,3-di-p-tolylallyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1b (20.6mg, 0.1mmol) and 2s (39.6mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 5c as a white solid in a yield (37%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.68(d, J=8.4Hz, 2H), 7.19(d, J=8.0Hz, 2H), 7.07(d, J=8.4Hz, 2H), 6.95(d , J=8.0Hz, 2H), 6.86(d, J=8.0Hz, 2H), 6.66(d, J=8.0Hz, 4H), 6.55(d, J=8.4Hz, 2H), 6.40(s, 1H ), 5.20(d, J=7.2Hz, 1H), 4.72(d, J=7.2Hz, 1H), 3.32(q, J=7.2Hz, 4H), 2.35(s, 3H), 2.28(s, 3H ), 2.22(s, 3H), 1.14(t, J=6.8Hz, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ147.3, 143.1, 139.2, 138.0, 137.1, 136.5, 135.0, 133.5, 129.4, 129.3, 129.3, 129.1, 128.8, 128.6, 127.4, 125.6, 111.7, 64.0, 44.4, 21.5, 21.3, 21.2, 12.6. HRMS (ESI) calcd. for C ₃₄ H ₃₉ N ₂ O ₂ S ([M+H] ⁺ )539.2727, Found 539.2730.HPLC condition: ChiralpakAD-H column, n-hexane/i-PrOH=90:10, 1.0mL/min, 254 nm, t _r-major ＝10.9min, t _r-minor ＝16.1min , 87%ee. (c 0.5, CHCl ₃ ).

Example 35:

Synthesis of (S, E)-N-(1-(4-(Diethylamino)phenyl)-2,3-bis(4-ethylphenyl)allyl)-4-methylbenzonesulfonamide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1e (23.4mg, 0.1mmol) and 2s (39.6mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 5d as a white solid, the yield (60%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.70(d, J=7.6Hz, 2H), 7.20(d, J=7.6Hz, 2H), 7.09(d, J=7.6Hz, 2H), 6.99(d , J=7.6Hz, 2H), 6.89(d, J=7.6Hz, 2H), 6.69(d, J=7.6Hz, 4H), 6.56(d, J=8.0Hz, 2H), 6.41(s, 1H ), 5.22(d, J=7.6Hz, 1H), 4.77(d, J=7.2Hz, 1H), 3.33(q, J=6.8Hz, 4H), 2.59(q, J=7.6Hz, 2H), 2.53(q, J=7.6Hz, 2H), 2.35(s, 3H), 1.21(t, J=7.6Hz, 3H), 1.18-1.10(m, 9H). ¹³ C NMR (100MHz, CDCl ₃ )δ147 .4, 143.5, 143.1, 142.9, 139.2, 138.0, 135.3, 133.8, 129.5, 129.4, 129.3, 129.0, 128.6, 128.1, 127.5, 127.4, 125.7, 111.8, 64.1, 44.5, 28.2, 12.6, 28.6 , 12.6. HRMS (ESI) calcd. for C ₃₆ H ₄₃ N ₂ O ₂ S ([M+H] ⁺ ) 567.3040, Found 567.3044.HPLC condition: Chiralpak AD-H column, n-hexane/i-PrOH=90 : 10, 1.0mL/min, 254nm, t _r-major = 8.5min, t _r-minor = 10.6min, 90% ee. (c 1.0, CHCl ₃ ).

Example 36:

Synthesis of (S, E)-N-(1-(4-(Diethylamino)phenyl)-2,3-bis(4-methoxyphenyl)allyl)-4-methylbenzenesulfona mide

In a nitrogen atmosphere, ligands AnIPr-1 (9.4mg, 10mol%), t-BuOK (1.4mg, 12mol%), Ni(cod) ₂ (2.8mg, 10mol%), THF were added sequentially to the reaction flask (1.5mL), i-PrOH (1.5mL), finally added raw materials 1f (23.8mg, 0.1mmol) and 2s (39.6mg, 0.12mmol), stirred at 60°C for 18 hours, cooled to room temperature, added ethyl acetate to dilute , filtered with celite, concentrated and separated by column chromatography to obtain the target product 5e as a white solid, the yield (28%). ¹ H NMR (400MHz, CDCl ₃ ) δ7.69(d, J=8.4Hz, 2H), 7.19(d, J=8.0Hz, 2H), 7.06(d, J=8.8Hz, 2H), 6.71(d , J=8.8Hz, 2H), 6.69(s, 4H), 6.60(d, J=8.8Hz, 2H), 6.55(d, J=8.8Hz, 2H), 6.37(s, 1H), 5.18(d , J=7.2Hz, 1H), 4.72(d, J=7.2Hz, 1H), 3.76(s, 3H), 3.72(s, 3H), 3.32(q, J=7.2Hz, 4H), 2.35(s , 3H), 1.14 (t, J=7.2Hz, 6H). ¹³ C NMR (100MHz, CDCl ₃ ) δ158.9, 158.3, 147.3, 143.1, 138.0, 137.8, 130.7, 130.5, 130.3, 129.4, 129.1, 128.5 , _128.4 , _127.5 , _125.6 , ^114.1 , 113.3, 111.7, 64.1, 55.2, 44.4, 21.6, 12.6 _. .HPLC condition: Chiralpak AD-Hcolumn, n-hexane/i-PrOH=85:15, 1.0mL/min, 254nm, t _r-major ＝13.8min, t _r-minor ＝19.5min, 75%ee. (c 0.5, CHCl ₃ ).

Claims (10)

1. The preparation method of efficiently synthesizing allylamine derivatives is characterized in that the concrete steps of the method are: In nitrogen atmosphere, add ligand (ligand), base (base), metal catalyst M _m X _n , solvent (solvent) and alcohol (alcohol) to the reaction flask in sequence, and finally add raw material 1 and raw material 2 at the specified temperature Stir for 18 hours, cool to room temperature, filter through celite, concentrate, and separate by column chromatography to obtain the target product. 2. The metal catalyst involved in the present invention is Ni(cod) ₂ . 3. The nitrogen heterocyclic carbene ligand involved in the present invention can be an alkyl-substituted carbene ligand, such as cyclohexyl, methyl, tert-butyl, etc., or an aryl-substituted carbene ligand, such as 2 , 6-diisopropylphenyl substituted or 2,4,6-trimethylphenyl substituted, can be a benzoquinone skeleton electron-withdrawing carbene ligand, or an acenaphthoquinone skeleton electron-donating carbene ligand; It can be a chiral carbene ligand, and the chiral source can be a chiral alkylamine or a chiral aniline. When the chiral carbene ligand is an acenaphthoquinone skeleton and the chiral source is chiral aniline, the para-position R substituent of the chiral aniline can be methyl or tert-butyl; the aniline side chain aryl substituent can be phenyl or May be 3,5-dimethyl-substituted phenyl. 4. The alkali used in the present invention is potassium tert-butoxide, etc., but not limited thereto. 5. The alcohol involved in the present invention can be primary alcohols such as methanol, ethanol, n-propanol, benzyl alcohol, or isopropanol, 1-phenylethanol, 2,4-dimethyl-3-pentanol, Secondary alcohols such as 2-methylcyclohexanol, but not limited to these. 6. The solvent used in the present invention can be tetrahydrofuran, benzene, toluene, xylene, mesitylene, trifluorotoluene, DMF, ethyl acetate, etc., tetrahydrofuran is optimal, and the corresponding application amount is 5-10 mL per millimole of raw material 1. 7. The reaction temperature involved in the present invention can be in the range of 60°C to 140°C, and 100°C or 60°C for some products is optimal. 8. The raw material 1 used in the present invention can be a symmetrical alkyl alkyne or a symmetrical aryl alkyne, and the aryl substituent can be at the aryl ortho, meta, or para position, and the substituent can be methyl, acetylene Donating groups such as radicals and methoxy groups may also be electron-withdrawing groups such as fluorine or trifluoromethyl; it may also be an asymmetric alkylaryl alkyne, or an asymmetric alkyl alkyne. 9. ^The R substituent in the raw material 2 used in the present invention can be p-methylphenyl or tert-butyl, the ^R substituent can be aryl or alkyl, and the alkyl can be cyclohexyl or tert-butyl etc., but not limited to these; the aryl group can be phenyl, naphthyl and thiophene substituents, wherein the substituents on the aryl group can be in the ortho, meta, para position, and can be methyl, methoxy, N , N-dimethyl group, etc., may also be electro-absorbing fluorine, trifluoromethyl group, etc., but not limited to these groups. 10. The R substituent in the product ³ of the present invention can be p-methylphenyl or tert ^- butyl, the ^R substituent can be ^an alkyl or aryl substituent, R and R can be the same, can be the same It can be an aryl group or both can be an alkyl group, R ¹ and R ² can also be different, can be an aryl group and an alkyl group, or can be different alkyl groups, and the above are not limited to these groups.