A method for the catalytic preparation of chiral 2-(1,3-diarylallyl)malonates using palladium / phosphine oxabidentate phosphine ligands

Abstract

The application belongs to the field of organic synthesis, and discloses a method for preparing chiral 2-(1,3-diarylallyl)malonate by using a Pd / phosphine oxygen bidentate phosphine phenol ligand catalysis, which comprises the following steps: under a protective atmosphere, mixing P, O-bidentate phosphine phenol ligand, a palladium catalyst, N, O-bis(trimethylsilyl)acetamide, a malonate nucleophilic reagent and an allyl acetate electrophilic reagent in dichloromethane, and reacting to obtain chiral 2-(1,3-diarylallyl)malonate product. The system has the advantages of high enantioselectivity, high catalytic efficiency, wide substrate application range and mild conditions.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, and specifically to a method for preparing chiral 2-(1,3-diarylallyl)malonate using palladium / phosphobisdentate phosphonophenol ligand catalysis. Background Technology

[0002] Chiral 2-(1,3-diarylallyl)malonates are a representative class of chalcone skeleton products containing multiple convertible functional groups, which can be derived into chiral compounds with important application prospects through various pathways. First, these compounds can undergo decarboxylation under alkaline catalysis to generate β,γ-unsaturated ketones [J. Org. Chem. 2025, 90, 16845-16856]. This type of skeleton is widely found in natural products and bioactive molecules, and can serve as an important intermediate in the total synthesis of natural products, as well as an industrial raw material for the preparation of vitamin E and its derivatives, thus possessing significant economic value. Second, these chiral malonates can be converted into chiral ester derivatives through diastereoconvergence, a key step in the synthesis of highly selective antimuscarinic agents [Org. Lett. 2014, 16, 1570-1573]. Antimuscarinic agents are widely used clinically to treat diseases such as overactive bladder and gastric cramps, thus this transformation pathway has important reference value for new drug development. Furthermore, the chiral allyl malonate skeleton itself is a key structural fragment of many antiviral active molecules. Studies have shown that structural integration with aromatic heterocyclic side chains can yield candidate compounds with good inhibitory activity against plant viruses such as tobacco mosaic virus and cucumber mosaic virus [a)Bioorg. Med. Chem. Lett. 26(2016) 168–173; b)RSC Adv., 2020, 10, 24483–24490], demonstrating its application potential in the field of pesticide chemistry. Finally, its oxidation products are an important class of chiral synthetic building blocks, which can be further used to construct complex molecules containing core structures such as chiral pyrrole and cyclopropane [a)Chem. Commun., 2016, 52, 13097-13100; b)Org. Biomol.Chem., 2012, 10, 7863-7868]. These structural units are widely found in biologically active natural products and drug molecules, and have important value for synthetic chemistry research.

[0003] In summary, developing efficient and highly enantioselective synthetic methods to construct structurally diverse 2-(1,3-diarylallyl)malonates and their derivatives is not only of significant academic research importance but also provides valuable synthetic tools for fields such as medicinal chemistry, pesticide chemistry, and natural product synthesis. Currently, the synthesis of these chiral products mainly relies on palladium-catalyzed asymmetric allylic alkylation reactions. The high enantioselectivity of this reaction hinges on the design of chiral ligands. By coordinating with the palladium center, the ligand creates a specific chiral environment, thereby precisely controlling the direction of nucleophilic attack on the allyl palladium intermediate and ultimately achieving excellent enantioselectivity. To date, researchers have developed various types of chiral ligands for this reaction.

[0004] However, existing synthetic techniques still have the following shortcomings: the synthesis of most high-performance chiral ligands is cumbersome, requiring expensive raw materials or harsh reaction conditions, which limits their industrial application; some ligands exhibit significant differences in performance on different substrates, lacking universality; and the application of P,O-bidentate ligands based on the binaphthyl skeleton in palladium-catalyzed asymmetric allylic alkylation reactions has not yet been reported.

[0005] Therefore, developing a novel catalytic method with simple ligand structure, convenient synthesis, high catalytic efficiency, and excellent enantioselectivity has significant academic value and promising industrial application prospects. Summary of the Invention

[0006] This invention aims to solve the technical problems of expensive ligands, complex synthesis, and the need to improve enantioselectivity in the production of chiral 2-(1,3-diarylallyl)malonate esters generated by palladium-catalyzed asymmetric allyl alkylation reactions in the prior art. It provides a method for preparing chiral allyl alkylation products with high yield and high stereoselectivity using a P,O-bidententate phospho-phenol ligand with a specific structure.

[0007] The present invention achieves the above objectives by adopting the following technical solution: A method for preparing chiral 2-(1,3-diarylallyl)malonate using palladium / phosphobisdentate phosphonophenol ligand catalysis includes the following steps: under a protective atmosphere, P,O - Bisdentate phosphonol ligand, palladium catalyst precursor, N,O-bis(trimethylsilyl)acetamide, malonate nucleophile (B) and allyl acetate electrophile (A) are mixed in dichloromethane to give 2-(1,3-diarylallyl)malonate product (C). The synthesis route of the method is as follows:

[0008] The Ar in the allyl acetate electrophilic reagent (A) is selected from any one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methylphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-tert-butylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 3-bromophenyl, 3-trifluoromethylphenyl, 3-chlorophenyl, 2-trifluoromethylphenyl, 2-chlorophenyl, and 2-fluorophenyl.

[0009] The malonate nucleophile (B) is selected from diethyl malonate, dimethyl malonate, diisopropyl malonate, ditert-butyl malonate, and dibenzyl malonate, i.e., R is selected from any one of methyl, ethyl, isopropyl, tert-butyl, and benzyl.

[0010] The palladium catalyst precursor is selected from any one of allyl palladium chloride dimer, dibenzylacetone palladium, palladium acetate, and bis(tri-tert-butylphosphine)palladium.

[0011] The P,O-bisdentate phosphonophenol ligand is selected from any one of L1-L4 of the following structures;

[0012] The molar ratio of palladium catalyst precursor, P,O-bis-dentate phosphonophenol ligand, N,O-bis(trimethylsilyl)acetamide, malonate nucleophile, and allyl acetate electrophile is 0.1:0.05-0.15:2:1.2:1; the reaction temperature is room temperature; and the reaction time is 48-64 h.

[0013] Compared with the prior art, the present invention has the following advantages and features: (1) The ligand structure is novel and easy to prepare: This invention is the first to apply P,O-bidentose phosphonophenol ligands to the reaction for generating chiral 1,3-diarylallyl malonate, opening up new applications for this type of ligand. This type of ligand is commercially available ( R Using )-BINOL as a starting material, it can be easily synthesized in four steps. The synthetic route is short, the operation is simple, and the yield is high. It does not require expensive reagents or harsh reaction conditions, and has good practicality and scalability.

[0014] (2) High enantioselectivity: Under optimized reaction conditions, the enantioselectivity of the model substrate can reach 95%ee, which is significantly better than that of commercial ligands under the same conditions, demonstrating the significant advantages of the catalytic system of the present invention in stereochemical control.

[0015] (3) High catalytic efficiency: the target product yield is 70%-97%, and the amount of ligand can be as low as 5% of the amount of raw material a. It has excellent atom economy, reduces the cost of catalyst, and is conducive to industrial application.

[0016] (4) Wide range of substrates: Good to excellent enantioselectivity can be obtained for aryl-substituted substrates containing electron-donating and electron-withdrawing groups, as well as para-, meta-, and ortho-substituted substrates, demonstrating good substrate versatility and functional group tolerance.

[0017] Simple to operate and mild conditions: The reaction is carried out at room temperature, without the need for strict anhydrous conditions, and the post-processing is simple, making it suitable for large-scale preparation and industrial production. Attached Figure Description

[0018] The present invention will be further described below with reference to the accompanying drawings and embodiments: Figure 1 for( E HPLC chromatogram of the racemic mixture of diethyl 2-(1,3-diphenylallyl)malonate; Figure 2 The sample prepared in Example 5 ( R , E HPLC chromatogram of diethyl 2-(1,3-diphenylallyl)malonate; Figure 3 for( E HPLC chromatogram of the racemic mixture of dimethyl 2-(1,3-diphenylallyl)malonate; Figure 4 The sample prepared in Example 15 ( R , E HPLC chromatogram of dimethyl 2-(1,3-diphenylallyl)malonate. Detailed Implementation

[0019] Unless otherwise specified, the experimental methods described in the following embodiments are conventional methods, and the experimental reagents, materials, and equipment are all commercially available. The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the invention in any way.

[0020] Example 1 ( R )-2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol (L1) The preparation process is as follows:

[0021] Will( R1,1'-bi-2-naphthol (8.59 g, 30 mmol) and triethylamine (12.5 mL, 90 mmol) were dissolved in dichloromethane, and trifluoromethanesulfonic anhydride (11.0 mL, 66 mmol) was added at 0°C. The mixture was stirred at room temperature for 6 hours. After the reaction was complete, the solvent was evaporated, and the residue was diluted with ethyl acetate and washed successively with 5% hydrochloric acid, saturated sodium bicarbonate aqueous solution, and saturated brine. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was used directly in the next reaction without purification.

[0022] Under argon protection, compound S1 (2.2 g, 4.0 mmol), diphenylphosphine oxide (1.62 g, 8.0 mmol), 1,3-bis(diphenylphosphino)propane (dppp) (165 mg, 0.4 mmol), palladium acetate (90 mg, 0.4 mmol), and N,N-diisopropylethylamine (20 mmol) were dissolved in DMSO (40 mL), and the mixture was heated to 120 °C and stirred for 12 hours. After the reaction was complete, the solvent was removed by vacuum distillation. Water (50 mL) and ethyl acetate (20 mL) were added to the residue, and the organic phase was washed successively with 10% hydrochloric acid (3 × 50 mL), saturated brine, and distilled water, and then dried over anhydrous sodium sulfate. The crude product was used directly in the next reaction without purification.

[0023] Compound S2 (1.3 g, 2.0 mmol) was dissolved in a mixed solvent of 1,4-dioxane / methanol (2 / 1, 30 mL / 15 mL), and 3N sodium hydroxide aqueous solution (3.0 mL) was added at room temperature. The reaction mixture was stirred for 12 hours, then the pH was adjusted to 1 with concentrated hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was used directly in the next reaction without purification.

[0024] Under argon protection, in a three-necked round-bottom flask, compound S3 (2.0 mmol) and triethylamine (48 mmol, 2.1 mL) were dissolved in toluene (50 mL), and trichlorosilane (10 mmol, 1.0 mL) was slowly added at 0 °C. The mixture was heated to reflux and stirred for 18 hours. After the reaction was complete, the cooled mixture was added to diethyl ether and a saturated aqueous solution of sodium bicarbonate. The solid was removed by filtration, and the solvent was removed by vacuum distillation. The residue was purified by rapid column chromatography (stationary phase: silica gel; eluent: ethyl acetate / petroleum ether = 1 / 20) to give the product in 43% yield.

[0025] White solid, melting point 123-124°C o C; 1H NMR (400 MHz, Chloroform-d) δ 7.97 – 7.88(m, 3H), 7.84 – 7.77 (m, 1H), 7.51 (ddd, J = 8.2, 6.1, 1.9 Hz, 1H), 7.47 (dd,J = 8.6, 2.7 Hz, 1H), 7.32 – 7.27 (m, 7H), 7.25 – 6.99 (m, 8H), 6.75 (d, J =8.5 Hz, 1H), 4.57 (s, 1H). 13 C NMR (101 MHz, CDCl3) δ 150.07, 150.05, 137.6,137.5, 137.2, 136.4, 136.3, 135.8, 135.7, 132.9, 132.8, 132.8, 132.7, 132.6,132.5, 132.4, 132.2, 132.2, 129.24, 129.17, 128.1, 127.8, 127.6, 127.52,127.45, 127.3, 127.2, 127.1, 126.9, 126.2, 126.1, 125.3, 125.2, 125.2, 123.9, 122.2, 117.3, 117.2, 116.4. (Due to the complexity of C–P coupling, all signal peaks in the carbon NMR spectrum appear as single peaks.) 31 P NMR (162 MHz, Chloroform-d) δ -13.68. Example 2 ( R )-2'-(di-p-tolylphosphino)-[1,1'-binaphthyl]-2-phenol (L2) In addition to replacing diphenylphosphine oxide with di-p-tolylphosphine oxide, S2 is replaced with ( R )-2'-(di-p-tolyloxyphosphino)-[1,1'-binaphthyl]-2-yltrifluoromethanesulfonate, S3 replaced with ( R Except for 1,1'-binaphthyloxyphospho)-2'-phenol, the rest of the operation was the same as in Example 1, with a yield of 34%.

[0026] White solid, melting point 142-143°C o C; 1H NMR (400 MHz, Chloroform-d) δ 7.94 – 7.86(m, 3H), 7.79 (d, J = 8.2 Hz, 1H), 7.52 – 7.43 (m, 2H), 7.26 – 7.07 (m, 8H),7.04 – 6.96 (m, 1H), 6.87 – 6.96 (m, 4H), 6.73 (d, J = 8.4 Hz, 1H), 4.60 (s,1H), 2.33 (s, 3H), 2.25 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 151.12, 151.10,139.3, 139.2, 138.6, 138.22, 138.17, 137.9, 134.0, 133.9, 133.8, 133.7,133.6, 133.5, 133.4, 133.3, 133.2, 130.3, 130.2, 129.5, 129.4, 129.1, 129.0,128.9, 128.2, 127.9, 127.2, 127.1, 126.3, 126.23, 126.21, 125.0, 123.1, 118.5, 118.4, 117.5, 21.4, 21.3. (Due to the complexity of C–P coupling, all signal peaks in the carbon nuclear magnetic resonance spectrum appear as single peaks). 31 P NMR (162 MHz, Chloroform-d) δ -15.23. Example 3 ( R )-2'-(bis(naphthyl-2-yl)phosphino)-[1,1'-binaphthyl]-2-phenol (L3) In addition to replacing diphenylphosphine oxide with bis(naphthyl-2-yl)phosphine oxide, S2 is replaced with ( R )-2'-(bis(naphthyl-2-yl)oxyphosphino)-[1,1'-binaphthyl]-2-yltrifluoromethanesulfonate, S3 replaced with ( R Except for 1,1'-binaphthyl)-2'-(bis(naphthyl-2-yl)oxyphosphinyl)-[1,1'-binaphthyl]-2-phenol, the rest of the operation was the same as in Example 1, with a yield of 39%.

[0027] White solid, melting point 177-178°C o C; 1H NMR (400 MHz, Chloroform-d) δ 7.91 – 7.88(m,, 3H), 7.84 – 7.37 (m, 17H), 7.30– 7.27 (m, 3H), 7.04 (t, J = 7.4 Hz, 1H), 6.76 (t, J = 7.6 Hz, 1H), 6.68 (d, J = 8.4 Hz, 1H), 4.74 (s, 1H). 13 C NMR (101MHz, CDCl3) δ 151.1, 138.9, 138.5, 138.4, 138.3, 134.8, 134.7, 134.4, 134.1,134.08, 134.04, 133.9, 133.8, 133.5, 133.4, 133.30, 133.25, 133.2, 133.1,130.4, 130.3, 130.1, 130.0, 129.9, 129.8, 129.3, 128.8, 128.2, 128.10,128.08, 128.0, 127.79, 127.77, 127.7, 127.6, 127.4, 127.2, 126.7, 126.6, 126.32, 126.28, 126.25, 126.2, 126.0, 124.8, 123.2, 118.4, 118.3, 117.5. (Due to the complexity of C–P coupling, all signal peaks in the carbon NMR spectrum appear as singlets.) 31 P NMR (162 MHz, Chloroform-d) δ -12.28. Example 4 ( R )-2'-(bis(4-methoxyphenyl)phosphino)-[1,1'-binaphthyl]-2-phenol (L4) In addition to replacing diphenylphosphine oxide with di-p-methoxyphenylphosphine oxide, S2 is replaced with ( R )-2'-(di-p-methoxyphenylphosphine)-[1,1'-binaphthyl]-2-yltrifluoromethanesulfonate, S3 replaced with ( R Except for )-2'-(di-p-methoxyphenylphosphine)-[1,1'-binaphthyl]-2-phenol, the rest of the operation was the same as in Example 1, with a yield of 30%.

[0028] White solid, melting point 176-177°C o C; 1H NMR (500 MHz, Chloroform-d) δ 7.93 – 7.88(m, 3H), 7.79 (d, J = 8.1 Hz, 1H), 7.49 (dd, J = 8.2, 6.5 Hz, 1H), 7.44 (dd,J = 8.5, 2.8 Hz, 1H), 7.31 – 7.17 (m, 6H), 7.02 – 6.91 (m, 3H), 6.87 – 6.85(m, 2H), 6.68 – 6.63 (m, 3H), 4.58 (s, 1H), 3.80 (s, 3H), 3.73 (s, 3H). δ -16.38. 13 C NMR (101 MHz, CDCl3) δ 160.1, 159.9, 151.3, 135.3, 135.2, 135.1, 135.0, 130.2, 129.9, 128.9, 128.8, 128.2, 127.9, 127.0, 126.2, 125.1, 123.1, 117.7, 114.3, 114.0, 113.9, 55.4, 55.2. (Due to the complexity of C–P coupling, all signal peaks in the carbon NMR spectrum appear as singlets.) 31 P NMR (162 MHz, Chloroform-d) δ -16.36. Example 5 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate Under an argon atmosphere, allyl palladium chloride dimer (1.8 mg, 0.005 mmol) and ( R )-2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol (4.6 mg, 0.01 mmol). Dichloromethane (2 mL) was added, and the mixture was stirred at room temperature for 1 hour. Then, N,O-bis(trimethylsilyl)acetamide (49 μL, 0.2 mmol) was added to the solution. E1,3-Diphenylallyl-2-yl acetate (25 mg, 0.1 mmol) and diethyl malonate (18 μL, 0.12 mmol) were added. After addition, the mixture was stirred at room temperature for 48 hours. After the reaction, the mixture was filtered through diatomaceous earth, and the organic phase was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain the target product. The packing material was silica gel, and the eluent was V(petroleum ether):V(ethyl acetate) = 97:3, with a yield of 98% and an ee value of 86%. It was a colorless oil. High performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 9.7 min (major), 12.4 min (minor). 1 H NMR (400 MHz, Chloroform-d)δ 7.35 – 7.15 (m, 10H), 6.47 (d, J = 15.7 Hz, 1H), 6.34 (dd, J = 15.8, 8.5Hz, 1H), 4.26 (dd, J = 11.0, 8.5 Hz, 1H), 4.17 (q, J = 7.1 Hz, 2H), 4.02 –3.94 (m, 2H), 3.92 (d, J = 10.9 Hz, 1H), 1.20 (t, J = 7.1 Hz, 3H), 1.00 (t, J= 7.1 Hz, 3H).

[0029] Example 6 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate Except for replacing the allyl palladium chloride dimer with bis(dibenzylacetone)palladium and changing the amount of substance from 0.005 mmol to 0.01 mmol, the operation was the same as in Example 5, with a yield of 86% and an ee value of 52%.

[0030] Example 7 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate Except for replacing the allyl palladium chloride dimer with palladium acetate and changing the amount of substance from 0.005 mmol to 0.01 mmol, the other operations were the same as in Example 5, with a yield of 81% and an ee value of 66%.

[0031] Example 8 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate Except for replacing the allyl palladium chloride dimer with bis(tri-tert-butylphosphine)palladium and changing the amount of substance from 0.005 mmol to 0.01 mmol, the other operations were the same as in Example 5, with a yield of 82% and an ee value of 78%.

[0032] Example 9 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Except for replacing the amount of 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with 0.015 mmol, the rest of the operation was the same as in Example 5, with a yield of 99% and an ee value of 74%.

[0033] Example 10 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Except for replacing the amount of 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with 0.008 mmol, the rest of the operation was the same as in Example 5, with a yield of 98% and an ee value of 87%.

[0034] Example 11 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Except for replacing the amount of 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with 0.005 mmol instead of 0.01 mmol, the rest of the operation was the same as in Example 5, with a yield of 98% and an ee value of 92%.

[0035] Example 12 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Replace 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with the compound shown in L2. R The same procedure was performed as in Example 5, except that the amount of substance was changed from 0.01 mmol to 0.005 mmol, with a yield of 97% and an ee value of 87%.

[0036] Example 13 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Replace 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with the compound shown in L3. R The same procedure was performed as in Example 5, except that the amount of substance was changed from 0.01 mmol to 0.005 mmol, with a yield of 73% and an ee value of 89%.

[0037] Example 14 ( R , E Diethyl 2-(1,3-diphenylallyl)malonate In addition to the compound shown in L1 ( R Replace 2'-(diphenylphosphino)-[1,1'-binaphthyl]-2-phenol with the compound shown in L4. R The method used was 2'-(bis(4-methoxyphenyl)phosphino)-[1,1'-binaphthyl]-2-phenol, with the amount of substance changed from 0.01 mmol to 0.005 mmol. All other operations were the same as in Example 5, with a yield of 97% and an ee value of 95% (e.g., ...). Figure 2 (As shown).

[0038] Example 15 ( R , E Dimethyl 2-(1,3-diphenylallyl)malonate Except for replacing diethyl malonate with dimethyl malonate, the other operations were the same as in Example 14, with a yield of 93% and an ee value of 85% (e.g. Figure 4 (As shown).

[0039] Colorless oily substance. High performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 8 / 2 (volume ratio), flow rate 0.8 mL / min, retention times: 10.2 min (major), 14.1 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.35 – 7.26 (m, 8H), 7.25 – 7.17 (m, 2H), 6.48 (d, J = 15.7 Hz, 1H), 6.33 (dd, J = 15.7, 8.6 Hz, 1H), 4.27 (dd, J =11.0, 8.6 Hz, 1H), 3.96 (d, J = 11.0 Hz, 1H), 3.70 (s, 3H), 3.52 (s, 3H).

[0040] Example 16 (R , E 2-(1,3-diphenylallyl) diisopropyl malonate Except for replacing diethyl malonate with diisopropyl malonate, the other operations were the same as in Example 14, with a yield of 89% and an ee value of 86%.

[0041] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 8 / 2 (v / v), flow rate 0.8 mL / min, retention times: 7.9 min (major), 9.9 min (minor); ¹H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.26 (m, 7H), 7.24 – 7.15 (m, 3H), 6.47 (d, J = 15.8 Hz, 1H), 6.33 (dd, J = 15.7, 8.5 Hz, 1H), 5.03 (hept, J = 6.2 Hz, 1H), 4.82 (hept, J = 6.2 Hz, 1H), 4.24 (dd, J = 11.1, 8.5 Hz, 1H). Hz, 1H), 3.86 (d, J = 11.0 Hz, 1H), 1.22 (d, J = 6.2 Hz, 3H), 1.17 (d, J = 6.3 Hz, 3H), 1.05 (d, J = 6.2 Hz, 3H), 0.96 (d, J = 6.3 Hz, 3H).

[0042] Example 17 Except for replacing diethyl malonate with di-tert-butyl malonate and changing the reaction time from 48 h to 64 h, the other operations were the same as in Example 14, with a yield of 81% and an ee value of 90%.

[0043] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 8 / 2 (v / v), flow rate 0.8 mL / min, retention times: 7.1 min (major), 9.2 min (minor); ¹H NMR (400 MHz, Chloroform-d) δ 7.32 – 7.27 (m, 7H), 7.25 – 7.15 (m, 3H), 6.45 (d, J = 15.8 Hz, 1H), 6.33 (dd, J = 15.8, 8.3 Hz, 1H), 4.16 (dd, J = 11.0, 8.2 Hz, 1H), 3.74 (d, J = 11.0 Hz, 1H), 1.41 (s, 9H), 1.22 (s, 9H).

[0044] Example 18 Except for replacing diethyl malonate with dibenzyl malonate and changing the reaction time from 48 h to 64 h, the other operations were the same as in Example 14, with a yield of 91% and an ee value of 84%.

[0045] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 8 / 2 (v / v), flow rate 0.8 mL / min, retention times: 21.5 min (major), 26.6 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.2 – 7.17 (m, 18H), 7.05 – 7.04 (m, 2H), 6.41 (d, J = 15.8 Hz, 1H), 6.31 (dd, J = 15.7, 8.3 Hz, 1H), 5.13 – 5.07 (m,2H), 4.97 – 4.88 (m, 2H), 4.30 (dd, J = 10.8, 8.4 Hz, 1H), 4.04 (d, J = 10.8Hz, 1H).

[0046] Example 19 ( R , E Diethyl 2-(1,3-di-p-tolylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( EExcept for 1,3-di-p-tolyl-allyl-2-acetate, the operation was the same as in Example 14. Yield: 89%, ee value: 84%.

[0047] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 11.2 min (major), 15.2 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.20 – 7.17 (m, 4H), 7.11 – 7.05 (m,4H), 6.42 (d, J = 15.7 Hz, 1H), 6.26 (dd, J = 15.7, 8.5 Hz, 1H), 4.23 – 4.13(m, 3H), 3.98 (q, J = 7.0 Hz, 2H), 3.88 (d, J = 10.9 Hz, 1H), 2.29 (s, 6H), 1.19 (t, J = 7.1 Hz, 3H), 1.03 (t, J = 7.1 Hz, 3H).

[0048] Example 20 ( R , E Diethyl 2-(1,3-di-m-tolyl-allyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-m-tolyl-2-yl acetate, the operation was the same as in Example 14. Yield: 87%, ee value: 97%.

[0049] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 50 / 1 (v / v), flow rate 0.8 mL / min, retention times: 66.8 min (major), 74.5 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.23 – 7.06 (m, 6H), 7.03 – 7.00(m, 2H), 6.44 (d, J = 15.7 Hz, 1H), 6.30 (dd, J = 15.7, 8.6 Hz, 1H), 4.21(dd, J = 9.7, 7.3 Hz, 1H), 4.15 (q, J = 7.1 Hz, 2H), 4.03 – 3.95 (m, 2H), 3.90 (d, J = 11.0 Hz, 1H), 2.32 (s, 3H), 2.30 (s, 3H), 1.21 (t, J = 7.1 Hz,3H), 1.02 (t, J = 7.1 Hz, 3H).

[0050] Example 21 ( R , E Diethyl 2-(1,3-di-m-methoxyphenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-m-methoxyphenylallyl-2-yl acetate, the remaining operations were the same as in Example 14. Yield: 96%, ee value: 92%.

[0051] Colorless oil, yield 96%; ee = 92%; HPLC conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 8 / 2 (v / v), flow rate 0.8 mL / min, retention time: 9.9 min (major), secondary peak 16.0 min (minor); 1H NMR (400 MHz, Chloroform-d) δ 7.25 – 7.16(m, 2H), 6.93 – 6.83 (m, 4H), 6.78 – 6.74 (m, 2H), 6.45 (d, J = 15.7 Hz, 1H), 6.30 (dd, J = 15.7, 8.6 Hz, 1H), 4.23 (dd, J = 11.1, 8.6 Hz, 1H), 4.17 (q, J= 7.1 Hz, 2H), 4.03 – 3.96 (m, 2H), 3.91 (d, J = 11.1 Hz, 1H), 3.79 (s, 1H),3.78 (s, 1H), 1.21 (t, J = 7.1 Hz, 3H), 1.04 (t, J = 7.1 Hz, 3H).

[0052] Example 22 ( R , E Diethyl 2-(1,3-di-o-methoxyphenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-o-methoxyphenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 98%, ee value: 87%.

[0053] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 50 / 1 (v / v), flow rate 0.8 mL / min, retention times: 48.5 min (major), 63.9 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.38 (dd, J = 7.6, 1.7 Hz, 1H), 7.25 – 7.23 (m, 1H), 7.20 – 7.13 (m, 2H), 6.90 – 6.78 (m, 5H), 6.49 (dd, J =15.9, 9.0 Hz, 1H), 4.49 (t, J = 9.9 Hz, 1H), 4.24 (d, J = 10.7 Hz, 1H), 4.19– 4.11 (m, 2H), 3.98 – 3.92 (m, 2H), 3.87 (s, 3H), 3.78 (s, 3H), 1.20 (t, J =7.1 Hz, 3H), 1.00 (t, J = 7.1 Hz, 3H).

[0054] Example 23 ( R , E Diethyl 2-(1,3-di-tert-butylphenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-tert-butylphenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 76%, ee value: 60%.

[0055] Colorless oil, yield 76%; ee = 60%; HPLC conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 8.9 min (major), 11.3 min (minor); 1 H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.20 (m,8H), 6.46 (d, J = 15.7 Hz, 1H), 6.29 (dd, J = 15.8, 8.5 Hz, 1H), 4.26 – 4.12(m, 3H), 3.96 (q, J = 7.1 Hz, 2H), 3.89 (d, J = 10.9 Hz, 1H), 1.28 (s, 18H), 1.21 (t, J = 7.1 Hz, 3H), 0.96 (t, J = 7.1 Hz, 3H).

[0056] Example 24 ( R ,E Diethyl 2-(1,3-dichlorophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-p-chlorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 97%, ee value: 96%.

[0057] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 17.7 min (major), 26.3 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.44 (dd, J = 7.2, 2.3 Hz, 1H),7.39 (dd, J = 7.9, 1.4 Hz, 1H), 7.35 – 7.29 (m, 2H), 7.25 – 7.11 (m, 4H),6.90 (d, J = 15.7 Hz, 1H), 6.32 (dd, J = 15.7, 8.6 Hz, 1H), 4.20 (q, J = 7.1Hz, 2H), 4.12 (d, J = 10.7 Hz, 1H), 4.07 – 3.99 (m, 2H), 1.23 (t, J = 7.1 Hz,3H), 1.06 (t, J = 7.1 Hz, 3H).

[0058] Example 25 ( R , E Diethyl 2-(1,3-(di-p-fluorophenylallyl)malonate) In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-p-fluorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 98%, ee value: 96%.

[0059] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 10.9 min (major), 17.2 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.29 – 7.25 (m, 4H), 7.09 – 6.86(m, 4H), 6.41 (d, J = 15.7 Hz, 1H), 6.22 (dd, J = 15.7, 8.5 Hz, 1H), 4.27 –4.21 (m, 1H), 4.17 (q, J = 7.2 Hz, 2H), 4.03 – 3.95 (m, 2H), 3.85 (d, J =10.9 Hz, 1H), 1.20 (t, J = 7.1 Hz, 3H), 1.04 (t, J = 7.1 Hz, 3H).19F NMR (377MHz, Chloroform-d) δ -114.05 – -114.68 (m, 1F), -115.35 – -115.43 (m, 1F).

[0060] Example 26 ( R , E Diethyl 2-(1,3-di-p-bromophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-p-bromophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 93%, ee value: 95%.

[0061] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 17.2 min (major), 26.9 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.48 – 7.34 (m, 4H), 7.21 – 7.12(m, 4H), 6.38 (d, J = 15.8 Hz, 1H), 6.28 (dd, J = 15.7, 8.3 Hz, 1H), 4.25 –4.20 (m, 1H), 4.17 (q, J = 7.0 Hz, 2H), 4.04 – 3.96 (m, 2H), 3.85 (d, J =10.9 Hz, 1H), 1.20 (t, J = 7.1 Hz, 3H), 1.06 (t, J = 7.1 Hz, 3H).

[0062] Example 27 ( R , E Diethyl 2-(1,3-(di-p-trifluoromethylphenyl)allyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-p-trifluoromethylphenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 95%, ee value: 96%.

[0063] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 15.7 min (major), 22.3 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.60 (d, J = 8.1 Hz, 2H), 7.53 (d, J= 8.1 Hz, 2H), 7.45 – 7.39 (m, 4H), 6.52 (d, J = 15.8 Hz, 1H), 6.42 (dd, J =15.8, 8.3 Hz, 1H).4.36 (dd, J = 10.8, 8.2 Hz, 1H), 4.19 (q, J = 7.1 Hz, 2H),4.03 – 3.97 (m, 2H), 3.93 (d, J = 10.8 Hz, 1H), 1.21 (t, J = 7.1 Hz, 3H),1.04 (t, J = 7.1 Hz, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -62.57(s, 1F), -62.58(s, 1F).

[0064] Example 28 ( R , E Diethyl 2-(1,3-di-m-fluorophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-m-fluorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 98%, ee value: 96%.

[0065] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 9.4 min (major), 12.5 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.20 (m, 2H),7.09 – 7.05 (m,2H), 7.04 – 6.99 (m, 2H), 6.98 – 6.86 (m, 2H), 6.44 (d, J = 15.7 Hz, 1H), 6.31 (dd, J = 15.7, 8.5 Hz, 1H), 4.26 (dd, J = 10.8, 8.5 Hz, 1H), 4.18 (q, J= 7.1 Hz, 2H), 4.04 – 3.98 (m, 2H), 3.88 (d, J = 10.8 Hz, 1H), 1.21 (t, J =7.1 Hz, 3H), 1.05 (t, J = 7.1 Hz, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -112.48 (td, J = 9.1, 5.9 Hz, 1F), -113.46 (td, J = 9.5, 6.1 Hz, 1F).

[0066] Example 29 ( R , E Diethyl 2-(1,3-di-m-bromophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-m-bromophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 94%, ee value: 93%.

[0067] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 8.5 min (major), 11.1 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.47 – 7.44 (m, 2H), 7.39 – 7.32 (m,2H), 7.28 – 7.10 (m, 4H), 6.40 (d, J = 15.7 Hz, 1H), 6.29 (dd, J = 15.7, 8.4Hz, 1H), 4.24 – 4.15 (m, 3H), 4.04 – 3.99 (m, 2H), 3.87 (d, J = 10.8 Hz, 1H), 1.21 (t, J = 7.1 Hz, 3H), 1.06 (t, J = 7.1 Hz, 3H).

[0068] Example 30 ( R , E Diethyl 2-(1,3-di-m-trifluoromethylphenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-m-trifluoromethoxyphenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 95%, ee value: 97%.

[0069] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 5.3 min (major), 7.4 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.57 – 7.39 (m, 8H), 6.52 (d, J =15.9 Hz, 1H), 6.40 (dd, J = 15.8, 8.4 Hz, 1H), 4.36 (t, J = 9.6 Hz, 1H), 4.19(q, J = 7.1 Hz, 2H), 3.99 (q, J = 7.2 Hz, 2H), 3.93 (d, J = 10.7 Hz, 1H), 1.22 (t, J = 7.1 Hz, 3H), 1.02 (t, J = 7.1 Hz, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -62.63(s, 3F), -62.81(s, 3F).

[0070] Example 31 (R , E Diethyl 2-(1,3-dichlorophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-dichlorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 97%, ee value: 94%.

[0071] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 8.1 min (major), 10.4 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.27 (m, 2H), 7.26 – 7.21(m, 2H), 7.21 – 7.13 (m, 4H), 6.42 (d, J = 15.8 Hz, 1H), 6.31 (dd, J = 15.7,8.4 Hz, 1H), 4.24 – 4.14 (m, 3H), 4.02 (q, J = 7.1 Hz, 2H), 3.87 (d, J = 10.8Hz, 1H), 1.21 (t, J = 7.1 Hz, 3H), 1.06 (t, J = 7.1 Hz, 3H).

[0072] Example 32 ( R , E Diethyl 2-(1,3-di-o-trifluoromethylphenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-o-trifluoromethylphenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 70%, ee value: 65%.

[0073] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 5.5 min (major), 8.6 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.68 (d, J = 7.9 Hz, 1H), 7.58 –7.41 (m, 5H), 7.37 – 7.26 (m, 2H), 6.78 (d, J = 15.7 Hz, 1H), 6.24 (dd, J =15.6, 7.9 Hz, 1H), 4.80 (dd, J = 10.7, 7.9 Hz, 1H), 4.22 (q, J = 7.1 Hz, 2H), 4.06 (d, J = 10.7 Hz, 1H), 3.97 (q, J = 7.1 Hz, 2H), 1.25 (t, J = 7.1 Hz,3H), 0.99 (t, J = 7.1 Hz, 3H). 19 F NMR (376 MHz, Chloroform-d) δ -58.52(s,3F), -59.73(s,3F).

[0074] Example 33 ( R , E Diethyl 2-(1,3-di-o-chlorophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-o-chlorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 73%, ee value: 67%.

[0075] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 7.2 min (major), 9.2 min (minor). 1H NMR (400 MHz, Chloroform-d) δ 7.47 – 7.28 (m, 4H), 7.25 – 7.10 (m,4H), 6.90 (d, J = 15.7 Hz, 1H), 6.32 (dd, J = 15.7, 8.6 Hz, 1H), 4.86 (t, J =9.6 Hz, 1H), 4.20 (q, J = 7.1 Hz, 2H), 4.12 (d, J = 10.7 Hz, 1H), 4.07 – 3.99(m, 2H), 1.23 (t, J = 7.2 Hz, 3H), 1.06 (t, J = 7.1 Hz, 3H).

[0076] Example 34 ( R , E Diethyl 2-(1,3-di-o-fluorophenylallyl)malonate In addition to ( E Replace 1,3-diphenylallyl-2-yl acetate with ( E Except for 1,3-di-o-fluorophenylallyl-2-yl acetate, the operation was the same as in Example 14. Yield: 94%, ee value: 95%.

[0077] Colorless oily substance. High-performance liquid chromatography (HPLC) conditions: Daicel Chiralpak AD-H chiral column, n-hexane / isopropanol = 7 / 3 (v / v), flow rate 0.8 mL / min, retention times: 13.6 min (major), 15.8 min (minor). 1 H NMR (400 MHz, Chloroform-d) δ 7.41 – 7.37 (m, 1H), 7.33 – 7.29(m, 1H), 7.24 – 7.13 (m, 2H), 7.12 – 6.92 (m, 4H), 6.68 (d, J = 15.9 Hz, 1H), 6.47 (ddd, J = 15.9, 8.9, 1.4 Hz, 1H), 4.49 (dd, J = 11.1, 8.8 Hz, 1H), 4.19(q, J = 7.1 Hz, 2H), 4.08 (d, J = 11.1 Hz, 1H), 4.03 – 3.95 (m, 2H), 1.22 (t,J = 7.1 Hz, 3H), 1.03 (t, J = 7.1 Hz, 3H). 19F NMR (377 MHz, Chloroform-d) δ -114.28 – 114.35 (m, 1F), -115.35 – 115.43 (m, 1F).

[0078] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing chiral 2-(1,3-diarylallyl)malonate using palladium / phosphobisdentate phosphonophenol ligand catalysis, characterized in that, Includes the following steps: Under a protective atmosphere, P,O - Bisdentate phosphonol ligand, palladium catalyst precursor, N,O-bis(trimethylsilyl)acetamide, malonate nucleophile (B) and allyl acetate electrophile (A) are mixed in dichloromethane to give 2-(1,3-diarylallyl)malonate product (C). The synthesis route of the method is as follows: 。 2. The method according to claim 1, characterized in that, The Ar in the allyl acetate electrophilic reagent (A) is selected from any one of phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methylphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-tert-butylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 3-bromophenyl, 3-trifluoromethylphenyl, 3-chlorophenyl, 2-trifluoromethylphenyl, 2-chlorophenyl, and 2-fluorophenyl.

3. The method according to claim 1, characterized in that, The malonate nucleophile (B) is selected from diethyl malonate, dimethyl malonate, diisopropyl malonate, ditert-butyl malonate, and dibenzyl malonate, i.e., R is selected from any one of methyl, ethyl, isopropyl, tert-butyl, and benzyl.

4. The method according to claim 1, characterized in that, The palladium catalyst precursor is selected from any one of allyl palladium chloride dimer, dibenzylacetone palladium, palladium acetate, and bis(tri-tert-butylphosphine)palladium.

5. The method according to claim 1, characterized in that, The P,O-bisdentate phosphonophenol ligand is selected from any one of the following structures, L1-L4: 。 6. The method according to claim 1, characterized in that, The molar ratio of the palladium catalyst precursor, P,O-bis(trimethylsilyl)acetamide, malonic acid ester nucleophile, and allyl acetate electrophile is 0.1:0.05-0.15:2:1.2:

1.

7. The method according to claim 1, characterized in that, The reaction temperature was room temperature.

8. The method according to claim 1, characterized in that, The reaction time is 48-64 h.

9. The method according to claim 1, characterized in that, The protective atmosphere is a nitrogen or argon atmosphere.

10. The chiral 2-(1,3-diarylallyl)malonate prepared by the method according to any one of claims 1-9.

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