A method for synthesizing tetrasubstituted-1,3-alkenedicarboxylic acid

Abstract

The invention relates to a method for synthesizing tetrasubstituted ‑1,3‑enedicarboxylic acid, and discloses a method for synthesizing tetrasubstituted ‑1,3‑enedicarboxylic acid. The method comprises the following steps: using 1,3‑enyne and iodide as raw materials, potassium formate as a formate source, DABCO as a hydrogen transfer catalyst, Ir(bpy)2(dtbpy)PF6 as a photocatalyst, and cesium carbonate as a base, introducing CO2 under normal pressure, and obtaining an enedicarboxylic acid compound with an excellent to good yield under room temperature and visible light irradiation for 24 hours. The method has mild reaction conditions, good regioselectivity, and good functional group tolerance, and makes up for many deficiencies of the prior art.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a method for synthesizing tetrasubstituted-1,3-allenedicarboxylic acid. Background Art

[0002] Allenes are a class of compounds with 1,2-cumulant diene structures. After decades of research by chemists, allene chemistry has made great progress and has become a very important branch of organic chemistry. Many natural products containing allene structural fragments have also been isolated. More than 200 natural products containing allene fragments have been discovered so far. Allenes can be used as intermediates in the synthesis of dyes, drugs, additives, etc. Its polymers and copolymers can be used in paints, fibers and other industries. The status of allenes in organic synthetic chemistry is also getting higher and higher. In recent years, allene chemistry has become one of the research hotspots in organic chemistry. The synthesis of allenes, especially the synthesis of allene carboxylic acids, has always been a very important part of allene chemistry. Allene carboxylic acid compounds also have many applications in synthesis. Due to the challenges of their synthesis, there is a need to modify the substrate in advance, there are many steps, and the use of precious metal reagents, so organic chemists have not explored allene carboxylic acids. Based on this, the development of new and efficient methods for the synthesis of allene carboxylic acids can further expand the application of allene carboxylic acid compounds, which is of great significance in drug discovery and drug modification. Summary of the invention

[0003] The purpose of the present invention is to overcome the defects of the existing preparation technology and provide a method for synthesizing tetrasubstituted-1,3-allenedicarboxylic acid with high efficiency, mild conditions and good substrate universality.

[0004] The technical scheme of the present invention is: 1,3-enyne, iodide, photocatalyst, hydrogen transfer catalyst, formate, and alkali are placed in a Schlenk tube, a solvent is added, carbon dioxide gas is introduced under normal pressure, and blue light and visible light are irradiated at room temperature to obtain tetrasubstituted-1,3-allenedicarboxylic acid, and the reaction formula is as follows:

[0005]

[0006] (1)R 1 Selected from phenyl, 4-phenylphenyl, 3-methylphenyl, 2-methylphenyl, 4-trifluoromethoxyphenyl, 4-chlorophenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-tert-butylphenyl, 3-thienyl, 2-naphthyl, 4-chlorophenethyl, 3-benzoyloxypropyl, 4-methoxybenzyloxypropyl, cyclohexyl;

[0007] (2)R 2Selected from 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-methylformatephenyl, 4-phenoxyphenyl, 4-isopropylphenyl, 4-phenoxyphenyl, 1-naphthyl;

[0008] (3) The photocatalyst used is selected from Ir(bpy)2(dtbpy)PF6, 4CzIPN, 4DPAIPN, fac-Ir(ppy)3, preferably Ir(bpy)2(dtbpy)PF6;

[0009] (4) the hydrogen transfer catalyst used is selected from DABCO, methyl thiosalicylate, cyclohexyl mercaptan, DIPEA, preferably DABCO;

[0010] (5) the base used is selected from cesium carbonate, sodium carbonate, potassium carbonate, cesium fluoride, preferably cesium carbonate;

[0011] (6) the formate used is selected from potassium formate, sodium formate, cesium formate, preferably potassium formate;

[0012] (7) The solvent used is selected from DMSO, toluene, tetrahydrofuran, DMF, acetonitrile, preferably DMSO. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] 1. Figure 1 It is the general formula for the synthesis of tetrasubstituted-1,3-alkenedicarboxylic acid;

[0014] 2. Figure 2 is the preparation reaction formula of compound 3a;

[0015] 3. Figure 3 is the preparation reaction formula of compound 3b;

[0016] 4. Figure 4 is the preparation reaction formula of compound 3c;

[0017] 5. Figure 5 is the preparation reaction formula of compound 3d;

[0018] 6. Figure 6 is the preparation reaction formula of compound 3e;

[0019] 7. Figure 7 is the preparation reaction formula of compound 3f;

[0020] 8. Figure 8 is the preparation reaction formula of compound 3g;

[0021] 9. Fig. 9 is the preparation reaction formula of compound 3h;

[0022] 10. Fig.10 is the preparation reaction formula of compound 3i;

[0023] 11. Fig.11 is the preparation reaction formula of compound 3j;

[0024] 12. Fig.12 is the preparation reaction formula of compound 3k;

[0025] 13. Fig.13 is the preparation reaction formula of compound 31;

[0026] 14. Fig.14 is the preparation reaction formula of compound 3m;

[0027] 15. Fig.15 is the preparation reaction formula of compound 4b;

[0028] 16. Fig.16 is the preparation reaction formula of compound 4c;

[0029] 17. Fig.17 is the preparation reaction formula of compound 4d;

[0030] 18. Fig.18 is the preparation reaction formula of compound 4e;

[0031] 19. Fig.19 is the preparation reaction formula of compound 4f;

[0032] 20. Fig. 20 is the preparation reaction formula of compound 4g;

[0033] twenty one. Fig.21 is the preparation reaction formula of compound 4h;

[0034] twenty two. Fig. 22 is the preparation reaction formula of compound 4i;

[0035] twenty three. Fig.23 is the preparation reaction formula of compound 4j;

[0036] twenty four. Fig.24 This is the reaction formula for the preparation of compound 4k. DETAILED DESCRIPTION

[0037] The present invention is further described below through specific embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments, and all technologies implemented based on the above content of the present invention belong to the scope of the present invention.

[0038] Implementation Case 1

[0039] Using 1,3-enyne compound 1a and iodobenzene 2a as raw materials (reaction formula 1)

[0040]

[0041] In a glove box, 1,3-enyne compound 1a (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3a.

[0042] The product detection data are as follows: white solid; yield 90%.

[0043] 1 H NMR (400MHz, DMSO-d6) δ13.08(s,2H),7.32(q,J=7.3,6.5Hz,5H),7.29–7.22(m,4H),3.69(s,2H); 13 C NMR (100MHz, DMSO-d6) δ219.03,165.99,165.56,138.20,131.72,128.92,128.54.128.46,128.33.128.24.126.62.106.08.104.39.34.73.

[0044] Implementation Case 2 Using 1,3-enyne compound 1b and iodobenzene 2a as raw materials (Reaction Formula 2)

[0045]

[0046] In a glove box, 1,3-enyne compound 1b (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3b.

[0047] The product detection data are as follows: white solid; yield 62%.

[0048] 1 H NMR (400MHz, DMSO-d6) δ13.09(s,2H),7.66(t,J=7.7Hz,4H),7.47(t,J=7.5Hz,2H),7.40(dd,J=13.9,7.7Hz,3H),7.31–7.16(m,5H),3.70(s,2H); 13 C NMR(101MHz,DMSO-d6)δ219.06,165.88,165.48,139.58,138.12,130.66,129 .05,128.97,128.86,128.29,127.75,126.73,126.70,126.57,104.53,34.70.

[0049] Implementation Case 3 Using 1,3-enyne compound 1c and iodobenzene 2a as raw materials (Reaction Formula 3)

[0050]

[0051] In a glove box, 1,3-enyne compound 1c (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-allenedicarboxylic acid product 3c.

[0052] The product detection data are as follows: white solid; yield 75%.

[0053] 1 H NMR (400MHz, DMSO-d6) δ13.05(s,2H),7.32–7.16(m,6H),7.11(dd,J=7.7,1.7Hz,2H),7.03(d,J=1.9Hz,1H),3.72–3.65(m,2H),2.25(s,3H); 13 C NMR(101MHz,DMSO-d6)δ218.97,166.02,165.59,138.30,137.56,131.61,129.04 ,128.95,128.87,128.35,128.32,126.63,125.69,106.16,104.24,34.69,21.09.

[0054] Implementation Case 4 Using 1,3-enyne compound 1d and iodobenzene 2a as raw materials (Reaction Formula 4)

[0055]

[0056] In a glove box, 1,3-enyne compound 1d (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3d.

[0057] The product detection data are as follows: white solid; yield 62%.

[0058] 1 H NMR (400MHz, DMSO-d6) δ12.99(s,2H),7.30–7.15(m,7H),7.11(td,J=7.3,1.7Hz,1H),6.86(dd,J=7.6,1.3Hz,1H),3.62(q,J=15.6Hz,2H),2.05(s,3H); 13 C NMR(101MHz,DMSO-d6)δ217.07,166.18,165.44,138.01,136.65,132.21,129.95 ,129.81,129.04,128.40,128.29,126.59,125.68,105.79,103.08,34.51,19.33.

[0059] Implementation Case 5 Using 1,3-enyne compound 1e and iodobenzene 2a as raw materials (Reaction Formula 5)

[0060]

[0061] In a glove box, 1,3-enyne compound 1e (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after 24 h of reaction, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3e.

[0062] The product detection data are as follows: white solid; yield 83%.

[0063] 1 H NMR (400MHz, DMSO-d6) δ13.18(s,2H),7.47–7.38(m,2H),7.37–7.33(m,2H),7.30–7.15(m,5H),3.69(s,2H); 13 C NMR (101MHz, DMSO-d6) δ219.13,165.74,165.30,148.14,138.03,131.09,130.42,128.91,128.32,126.65,121.04,105.00,34.63; 19 F NMR (377 MHz, DMSO) δ -56.87.

[0064] Implementation Case 6 Using 1,3-eneyne compound 1f and iodobenzene 2a as raw materials (Reaction Formula 6)

[0065]

[0066] In a glove box, 1,3-enyne compound 1f (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3f.

[0067] The product detection data are as follows: white solid; yield 83%.

[0068] 1 H NMR (400MHz, DMSO-d6) δ13.13(s,2H),7.41(d,J=8.3Hz,2H),7.33(d,J=8.6Hz,2H),7.29–7.14(m,5H),3.68(s,2H); 13 C NMR (101MHz, DMSO-d6) δ219.04,165.75,165.27,138.04,132.97,130.58,130.18,128.88,128.50,128.32,126.62,105.13,104.94,34.65.

[0069] Implementation Case 7 Using 1,3-enyne compound 1g and iodobenzene 2a as raw materials (Reaction Formula 7)

[0070]

[0071] In a glove box, 1 g (0.2 mmol) of 1,3-enyne compound, iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, and the mixture was evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 3 g of 1,3-allylenedicarboxylic acid product.

[0072] The product detection data are as follows: white solid; yield 80%.

[0073] 1 H NMR (400MHz, DMSO-d6) δ12.96 (s, 2H), 7.30–7.13 (m, 7H), 6.90 (d, J = 8.7Hz, 2H), 3.74 (s, 3H), 3.66 (s, 2H), 3.37 (s, 3H); 13 C NMR (101MHz, DMSO-d6) δ218.74,166.00,165.69,159.23,138.21,129.68,128.82,128.24,126.51,123.49,113.91,105.56,104.07,55.25,34.72.

[0074] Implementation Case 8 Using 1,3-eneyne compound 1h and iodobenzene 2a as raw materials (Reaction Formula 8)

[0075]

[0076] In a glove box, 1,3-enyne compound 1h (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 hours, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain the 1,3-allylenedicarboxylic acid product 3h.

[0077] The product detection data are as follows: white solid; yield 74%.

[0078] 1 HNMR (400MHz, DMSO-d6) δ13.06 (s, 2H), 7.35–7.15 (m, 4H), 6.47 (s, 2H), 3.69 (d, J = 3.5Hz, 6H); 13 C NMR (101MHz, DMSO-d6) δ218.94,165.96,165.37,160.37,138.19,133.52,128.96,128.40,126.69,106.74,106.11,104.57,100.12,55.37,34.72.

[0079] Example 9 Using 1,3-enyne compound 1i and iodobenzene 2a as raw materials (reaction formula 9)

[0080]

[0081] In a glove box, 1,3-enyne compound 1i (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3i.

[0082] The product detection data are as follows: white solid; yield 83%.

[0083] 1 H NMR (400MHz, DMSO-d6) δ13.01 (s, 2H), 7.35 (d, J = 8.1Hz, 2H), 7.32–7.15 (m, 7H), 3.67 (s, 2H), 1.26 (s, 9H); 13 C NMR (101MHz, DMSO-d6) δ218.90,166.00,165.64,150.77,138.20,128.90,128.72,128.30,128.24,126.58,125.23,104.15,34.73,34.41,31.12.

[0084] Example 10 Using 1,3-eneyne compound 1j and iodobenzene 2a as raw materials (reaction formula 10)

[0085]

[0086] In a glove box, 1,3-enyne compound 1j (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3j.

[0087] The product detection data are as follows: white solid; yield 80%.

[0088] 1 H NMR (400MHz, DMSO-d6) δ13.00 (s, 2H), 7.68 (dd, J = 3.0, 1.2Hz, 1H), 7.50 (dd, J = 5. 1,3.0Hz,1H),7.36–7.13(m,5H),6.95(dd,J=5.1,1.3Hz,1H),3.73–3.64(m,2H); 13 CNMR(101MHz,DMSO-d6)δ219.76,166.07,165.77,138.55,130.94,129.24,128.66,127.66,126.93,126.52,124.59,105.12,102.13,35.13.

[0089] Example 11 Using 1,3-eneyne compound 1k and iodobenzene 2a as raw materials (reaction formula 11)

[0090]

[0091] In a glove box, 1,3-enyne compound 1k (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3k.

[0092] The product detection data are as follows: white solid; yield 62%.

[0093] 1 H NMR(400MHz,DMSO-d6)δ13.11(s,2H),7.92–7.82(m,4H),7.52(dt,J=6.2,3.6Hz,2H),7 .40(dd,J=8.5,1.9Hz,1H),7.36–7.25(m,4H),7.24–7.16(m,1H),3.74(d,J=2.3Hz,2H); 13 C NMR(101MHz,DMSO-d6)δ219.37,165.95,165.61,138.25,132.79,132.50,129.09,128.99, 128.37,128.14,127.88,127.61,127.45,126.66,126.60,126.28,106.23,104.78,34.73.

[0094] Example 12 Using 1,3-enyne compound 11 and iodobenzene 2a as raw materials (reaction formula 12)

[0095]

[0096] In a glove box, 1,3-enyne compound 1l (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 hours, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3l.

[0097] The product detection data are as follows: white solid; yield 65%.

[0098] 1 H NMR (400MHz, DMSO-d6) δ12.82(s,2H),7.95(dt,J=8.3,1.3Hz,2H),7.65(tdd,J=6.6,3.3,1.6Hz,1H),7.52(td,J=7.8,2.6Hz,2 H),7.31–7.11(m,5H),4.22(td,J=6.4,1.6Hz,2H),3.56(dd,J=3.4,1.9Hz,2H),2.39–2.17(m,2H),1.70(td,J=7.2,3.3Hz,2H); 13 C NMR(101MHz,DMSO-d6)δ216.66,166.41,166.33,165.72,138.41,133.34,129.20,128.84,128 .81,128.21,126.43,103.95,103.10,63.75,39.78,39.58,39.36,39.16,34.63,26.66,24.74.

[0099] Example 13: Using 1,3-eneyne compound 1m and iodobenzene 2a as raw materials (reaction formula 13)

[0100]

[0101] In a glove box, 1,3-enyne compound 1m (0.2 mmol), iodobenzene 2a (2 equiv., 45 μL), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 3m.

[0102] The product detection data are as follows: white solid; yield 60%.

[0103] 1 H NMR (400MHz, DMSO-d6) δ12.55(s,2H),7.13(dp,J=21.1,7.1,6.7Hz,5H),3.44(s,2H),2.09(tt,J=11.6, 3.4Hz,1H),1.63–1.38(m,5H),1.19–1.02(m,2H),0.97–0.73(m,2H),0.53(qd,J=12.8,12.2,3.7Hz,1H); 13 C NMR(101MHz,DMSO-d6)δ216.50,166.63,166.19,138.45,129.04,128.17, 126.42,109.41,104.70,36.86,34.66,31.90,31.35,25.82,25.73,25.67.

[0104] Example 14: Using 1,3-enyne compound 1a and aryl iodide 2b as raw materials (reaction formula 14)

[0105]

[0106] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2b (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4b.

[0107] The product detection data are as follows: white solid; yield 84%.

[0108] 1 H NMR (400MHz, DMSO-d6) δ12.93(s,2H),7.35–7.27(m,5H),7.14(d,J=8.1Hz,2H),7.05(d,J=7.8Hz,2H),3.63(s,2H),2.24(s,3H); 13 C NMR (101MHz, DMSO-d6) δ218.98,166.00,165.59,135.59,135.09,131.77,128.89,128.79,128.53,128.45,128.21,105.98,104.46,34.34,20.76.

[0109] Example 15 Using 1,3-enyne compound 1a and aryl iodide 2c as raw materials (reaction formula 15)

[0110]

[0111] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2c (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4c.

[0112] The product detection data are as follows: white solid; yield 79%.

[0113] 1 H NMR(400MHz, DMSO-d6)δ13.07(s,2H),7.36–7.29(m,5H),7.13(t,J=7.4Hz,1H), 7.05(d,J=2.8Hz,2H),6.99(d,J=7.5Hz,1H),3.63(d,J=4.2Hz,2H),2.19(s,3H); 13 CNMR(100MHz,DMSO-d6)δ219.07,165.96,165.55,138.02,137.34,131.75,129.58,128. 53,128.42,128.18,127.18,125.90,104.31,39.98,39.56,39.35,39.15,34.60,21.02.

[0114] Example 16 Using 1,3-enyne compound 1a and aryl iodide 2d as raw materials (Reaction Formula 16)

[0115]

[0116] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2d (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2 M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4d.

[0117] The product detection data are as follows: white solid; yield 85%.

[0118] 1 H NMR (400MHz, DMSO-d6) δ12.99(s,2H),7.32–7.14(m,7H),7.11(td,J=7.3,1.7Hz,1H),6.86(dd,J=7.6,1.3Hz,1H),3.62(q,J=15.6Hz,2H),2.05(s,3H); 13 C NMR(101MHz,DMSO-d6)δ217.07,166.18,165.44,138.01,136.65,132.21,129.95 ,129.81,129.04,128.40,128.29,126.59,125.68,105.79,103.08,34.51,19.33.

[0119] Example 17 Using 1,3-eneyne compound 1a and aryl iodide 2e as raw materials (Reaction Formula 17)

[0120]

[0121] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2e (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after 24 hours of reaction, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4e.

[0122] The product detection data are as follows: white solid; yield 75%.

[0123] 1 H NMR (400MHz, DMSO-d6) δ13.10 (s, 2H), 7.36–7.26 (m, 7H), 7.07 (t, J = 8.8Hz, 2H), 3.68 (s, 2H); 13 C NMR(101MHz,DMSO-d6)δ219.26,166.26,165.85,134.69,134.66,131.98,131 .13,131.05,128.82,128.79,128.57,115.43,115.22,106.57,104.86,34.21; 19 F NMR (377MHz, DMSO-d6) δ-116.44.

[0124] Example 18 Using 1,3-enyne compound 1a and aryl iodide 2f as raw materials (reaction formula 18)

[0125]

[0126] In a glove box, add 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2f (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) to a Schlenk tube (10 mL) equipped with a stirrer, and add 2 mL of ultra-dry DMSO. Remove the Schlenk tube from the glove box, evacuate and backfill with carbon dioxide three times. Irradiate the mixture with a 40W 460nm Kessil Blue LED (3 cm away, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, quench the reaction with hydrochloric acid (2 M) and extract with ethyl acetate five times. The combined organic layers are washed with brine and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4f.

[0127] The product detection data are as follows: white solid; yield 87%.

[0128] 1 H NMR (400MHz, DMSO-d6) δ12.95(s,2H),7.37–7.26(m,9H),3.68(s,2H); 13 C NMR (101MHz, DMSO-d6) δ218.95,165.90,165.49,137.33,131.61,131.31,130.80,128.52,128.31,128.27,106.26,104.21,34.03.

[0129] Example 19: Using 1,3-eneyne compound 1a and aryl iodide 2g as raw materials (reaction formula 19)

[0130]

[0131] In a glove box, 1,3-enyne compound 1a (0.2 mmol), 2 g (2 equiv.) of aryl iodide, Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, and the mixture was evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 4 g of 1,3-allenedicarboxylic acid product.

[0132] The product detection data are as follows: white solid; yield 75%.

[0133] 1 H NMR (400MHz, DMSO-d6) δ13.01(s,2H),7.36–7.27(m,5H),7.17(d,J=8.4Hz,2H),6.81(d,J=8.2Hz,2H),3.70(s,3H),3.60(s,2H); 13 C NMR (101MHz, DMSO-d6) δ218.88,165.94,165.53,157.99,131.74,129.95,129.91,128.46,128.41,128.15,113.68,105.95,104.67,55.08,33.86.

[0134] Example 20 Using 1,3-eneyne compound 1a and aryl iodide 2h as raw materials (reaction formula 20)

[0135]

[0136] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2h (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 hours, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4h.

[0137] The product detection data are as follows: white solid; yield 84%.

[0138] 1 H NMR (400MHz, DMSO-d6) δ13.12(s,2H),7.84(d,J=8.2Hz,2H),7.41(d,J=8.1Hz,2H),7.35–7.28(m,5H),3.82(s,3H),3.76(s,2H); 13 C NMR (101MHz, DMSO-d6) δ218.92,166.17,165.77,165.34,144.02,131.45,129.26,129.14,128.45,128.26,106.19,103.81,52.14,34.53.

[0139] Example 21 Using 1,3-eneyne compound 1a and aryl iodide 2i as raw materials (Reaction Formula 21)

[0140]

[0141] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2i (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4i.

[0142] The product detection data are as follows: white solid; yield 73%.

[0143] 1 H NMR(400MHz,DMSO-d6)δ12.94(s,2H),7.36–7.25(m,5H),7.17(d,J=7.8Hz,2H), 7.12(d,J=7.9Hz,2H),3.63(s,2H),2.83(h,J=7.0Hz,1H),1.16(d,J=7.0Hz,6H); 13 CNMR(101MHz,DMSO-d6)δ219.00,166.03,165.64,146.70,135.60,131.86,1 28.81,128.58,128.40,128.19,126.23,104.30,34.35,33.21,24.10,24.02.

[0144] Example 22 Using 1,3-eneyne compound 1a and aryl iodide 2j as raw materials (reaction formula 22)

[0145]

[0146] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2j (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 h, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo; the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4j.

[0147] The product detection data are as follows: white solid; yield 70%.

[0148] 1 H NMR (400MHz, DMSO-d6) δ13.01(s,2H),7.38–7.24(m,9H),7.09(t,J=7.4Hz,1H),6.96–6.86(m,4H),3.68(s,2H); 13 C NMR(101MHz,DMSO-d6)δ219.07,166.01,165.58,157.23,155.14,133.49,131.70, 130.60,130.09,128.47,128.25,123.28,118.92,118.27,106.31,104.86,34.03.

[0149] Example 23 Using 1,3-eneyne compound 1a and aryl iodide 2k as raw materials (reaction formula 23)

[0150]

[0151] In a glove box, 1,3-enyne compound 1a (0.2 mmol), aryl iodide 2k (2 equiv.), Ir(bpy)2(dtbpy)PF6 (1 mol%, 1.7 mg), DABCO (0.5 equiv., 11.2 mg), potassium formate (3 equiv., 50.5 mg), cesium carbonate (3.0 equiv., 195 mg) were added to a Schlenk tube (10 mL) equipped with a stirring bar, and 2 mL of ultra-dry DMSO was added. The Schlenk tube was removed from the glove box, evacuated and backfilled with carbon dioxide three times; the mixture was irradiated with a 40W 460nm Kessil Blue LED (at 3 cm, with a cooling fan to maintain the reaction temperature at room temperature); after reacting for 24 hours, the reaction was quenched with hydrochloric acid (2M) and extracted with ethyl acetate five times; the combined organic layers were washed with brine and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate / formic acid) to obtain 1,3-diene dicarboxylic acid product 4k.

[0152] The product detection data are as follows: white solid; yield 80%.

[0153] 1 H NMR (400MHz, DMSO-d6) δ13.00(s,2H),7.97(d,J=8.5Hz,1H),7.88(d,J=8.1Hz,1H),7.79(d ,J=8.0Hz,1H),7.50–7.34(m,4H),7.25–7.14(m,3H),7.02–6.92(m,2H),4.22–4.10(m,2H); 13 C NMR(101 MHz, DMSO-d6)δ219.03,166.04,165.31,134.16,133.41,131.51,131.43,128.42,128.32, 128.12,127.97,127.33,126.93,126.02,125.69,125.43,124.09,106.39,104.34,31.78.

Claims

1. A method for synthesizing tetrasubstituted-1,3-alkenedicarboxylic acid, characterized in that 1,3-enyne, iodide and carbon dioxide are used as substrates, Ir(bpy)2(dtbpy)PF6 is used as a photocatalyst, DABCO is used as a hydrogen transfer catalyst, cesium carbonate is used as a base, HCOOK is used as a formate, DMSO is used as a solvent, carbon dioxide gas is introduced under normal pressure, and tetrasubstituted-1,3-alkenedicarboxylic acid is obtained under blue light irradiation, and the reaction formula is as follows: in: R 1 is selected from phenyl, 4-phenylphenyl, 3-methylphenyl, 2-methylphenyl, 4-trifluoromethoxyphenyl, 4-chlorophenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-tert-butylphenyl, 3-thienyl, 2-naphthyl, 4-chlorophenethyl, 3-benzoyloxypropyl, 4-methoxybenzyloxypropyl, and cyclohexyl; R 2 Selected from 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-methylformylphenyl.

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