Alpha-furan boron compounds and three-component strategy synthesis method thereof

Abstract

The application provides an alpha-furan borane compound and a three-component strategy synthesis method thereof, the alpha-furan borane compound is synthesized by taking ketone compounds, alkyne aldehyde compounds and borane complexes as raw materials, and under the catalysis of cuprous chloride, and the alpha-furan borane compound is synthesized by one-step reaction. Compared with the prior art, the method has the advantages of economical steps, high atom utilization efficiency, green environmental protection and the like, and is a unique method for preparing the alpha-furan borane compound. In addition, the raw materials are convenient and easy to obtain, the operation steps are simple, the reaction conditions are mild, and the method is suitable for the needs of large-scale industrial production.

Description

Technical Field

[0001] This invention belongs to the field of fine chemical synthesis, specifically relating to an α-furan boron compound and its three-component synthetic method. Background Technology

[0002] Furan and boron structural units are important pharmacodynamic groups in drug molecules; therefore, the development of compounds possessing both furan and boron structural units is of significant research value. In 2017, the team led by Qilin Zhou at Nankai University reported a metal-catalyzed two-component synthesis method for α-furanborane compounds from conjugated acetylenones and boranes (J. Am. Chem. Soc. 2017, 139, 3784-3789). This method uses a conjugated acetylenone obtained by reacting a ketone and an acetylenal with additives such as acetic acid, piperidine, and magnesium sulfate, followed by post-treatment purification, as a starting material. Then, through the insertion of α-furan metal carbene into a boron-hydrogen bond, a series of α-furanborane compounds were synthesized.

[0003] Multicomponent cascade reactions offer advantages such as simple operation, high synthetic efficiency, and atom economy, making them a direct and effective route for constructing complex and diverse molecules. However, the complexity of the reactions and the diversity of products present significant challenges in designing synthons and screening conditions for this strategy. To date, there are no reports on the one-step synthesis of α-furan borane compounds via the insertion of α-furan metal carbene into a boron-hydrogen bond using a multicomponent strategy. Summary of the Invention

[0004] The purpose of this invention is to provide a synthetic method for α-furanborane compounds and their three-component strategy, overcoming the problems of cumbersome operation, low efficiency, and poor atom economy in existing technologies. This invention uses commercially available ketones, acetylacetic aldehydes, and borane complexes as raw materials, and synthesizes α-furanborane compounds in one step via an α-furan carbene boron-hydrogen bond insertion pathway under copper catalysis. The raw materials are readily available, the operation is simple, and the conditions are mild, making it suitable for large-scale industrial production.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] An α-furanborane compound, the structural formula of which is shown in formula (1):

[0007]

[0008] Among them, R 1 It is alkyl or aryl; R 2 For COME, COEt, CO2Me, or SO2Ph; R 3 It is alkyl or aryl; LB is NMe3, NMe(C4H8) or NMe(C5H) 10 ).

[0009] A three-component strategy for the synthesis of an α-furanborane compound involves using a ketone compound as shown in formula (2), an alkyne aldehyde compound as shown in formula (3), and a borane compound as shown in formula (4) in a one-step reaction catalyzed by cuprous chloride as shown in formula (5) to synthesize the α-furanborane compound as shown in formula (1).

[0010]

[0011] Further, the specific steps include: adding the catalyst CuCl and the reaction solvent sequentially to the reaction vessel under room temperature and air conditions, and stirring until homogeneous; then adding ketone compounds, acetylaldehyde compounds and borane complexes sequentially for reaction; after the reaction is completed, separating by silica gel column chromatography to obtain α-furanborane compounds.

[0012] Furthermore, the molar ratio of the ketone compound, acetylacetonate compound, borane complex and cuprous chloride is 1:1.5:4:0.1.

[0013] Furthermore, the reaction solvent is dichloromethane, and 0.4 mmol of ketone compound is added to every 1.0 mL of reaction solvent.

[0014] Furthermore, the reaction time is 10-20 hours.

[0015] Furthermore, the reaction temperature is 55°C.

[0016] Furthermore, after the reaction is complete, silica gel column chromatography is performed directly.

[0017] Furthermore, during separation by silica gel column chromatography, the eluents are petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 2:1 to 4:1.

[0018] Compared with the prior art, the present invention has the following beneficial technical effects:

[0019] The existing method for obtaining α-furanborane compounds uses conjugated alkynyl ketones obtained beforehand by reacting ketones and alkynyl aldehydes with additives such as acetic acid, piperidine, and magnesium sulfate, followed by post-processing purification. The synthesis of this raw material consumes a large amount of additives, has poor atom economy, and the post-processing process is also very time-consuming and labor-intensive.

[0020] This invention enables the one-step synthesis of α-furanborane compounds via a three-component strategy, avoiding the use of additives required for the raw material synthesis and the consumption of reagents for post-processing purification required by the two-component strategy. This saves time and labor costs, thus offering advantages such as being green and economical. Furthermore, the method of this invention uses readily available raw materials, is simple to operate, and operates under mild conditions, making it suitable for large-scale industrial production. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the reaction for synthesizing α-furanborane compounds using a three-component strategy. Detailed Implementation

[0022] The present invention will now be described in further detail:

[0023] An α-furanborane compound, as shown in formula (1), has the following structural formula:

[0024]

[0025] A three-component strategy for synthesizing α-furanborane compounds, such as Figure 1 As shown, the specific preparation scheme is as follows: using ketone compounds as shown in formula (2), acetylacetic aldehyde compounds as shown in formula (3) and borane compounds as shown in formula (4), under the catalysis of cuprous chloride as shown in formula (5), α-furanborane compounds as shown in formula (1) are synthesized in one step.

[0026]

[0027] A three-component strategy for synthesizing α-furanborane compounds includes: adding a catalyst CuCl and a reaction solvent dichloromethane sequentially to a reaction vessel under room temperature and air conditions, and stirring until homogeneous; then sequentially adding a ketone compound, an alkyne compound, and a borane complex, and reacting at 55°C; finally, separating directly by silica gel column chromatography, using petroleum ether:ethyl acetate as the eluent in a volume ratio of 2:1 to 4:1 to obtain the α-furanborane compound. The molar ratio of the ketone compound, alkyne compound, borane complex, and cuprous chloride catalyst is 1:1.5:4:0.1; the reaction solvent is dichloromethane, and 0.4 mmol of the ketone compound is added to every 1.0 mL of the reaction solvent; the reaction time is 10-20 hours.

[0028] The specific equation is as follows:

[0029]

[0030] The present invention will now be described in detail with reference to embodiments and accompanying drawings to facilitate a more comprehensive understanding of the invention by those skilled in the art, but this does not limit the invention to all embodiments. All other embodiments obtained without inventive effort are within the scope of protection of the present invention.

[0031] Example 1

[0032] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0033]

[0034] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1a (45.6 mg, 80% yield) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, v / v). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.32-7.26(m,2H),7.22(t,J=7.5Hz,2H),7.07(t,J=7 .2Hz,1H),6.29(s,1H),3.35(s,1H),2.50(s,3H),2.46(s,9H),2.35(s,3H). 13 C NMR (125MHz, CDCl3): δ195.0,160.9,156.1,147.4,128.5,128.3,124.6,122.1,104.6,52.6,38.0,29.2,14.6.

[0035] Example 2

[0036] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0037]

[0038] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3b (48.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1b (49.7 mg, yield 79%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.21(d,J=8.6Hz,2H),6.79(d,J=8.6Hz,2H),6.23(s,1 H),3.76(s,3H),3.30(t,J=4.9Hz,1H),2.50(s,3H),2.47(s,9H),2.34(s,3H). 13 C NMR (125MHz, CDCl3): δ195.0,161.3,157.0,156.3,139.4,129.2,122.2,113.8,104.3,55.4,52.7,36.8,29.3,14.6.

[0039] Example 3

[0040] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0041]

[0042] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3c (44.4 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1c (47.2 mg, yield 78%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1H NMR (500MHz, CDCl3): δ7.24-7.21(m,2H),6.91(t,J=8.7Hz,2H),6.26(s,3H),3.33(t,J=4.8Hz,1H),2.50(s,2H),2.48(s,9H),2.35(s,3H). 13 C NMR (125MHz, CDCl3): δ195.0, 160.7, 160.6 (d, J = 242.7Hz), 156.3, 143.0, 129.4 (d,J=7.6Hz),122.2,115.0(d,J=20.9Hz),114.9,104.7,52.7,37.0,29.3,14.6. 11 B NMR (160MHz, CDCl3): δ-1.1. 19 F NMR (471MHz, CDCl3): δ-119.8. High-resolution data: Calculated for [C 17 H 24 BFNO2,M+H] + :304.1879,found:304.1885.

[0043] Example 4

[0044] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0045]

[0046] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3d (43.2 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1d (47.2 mg, yield 79%) is obtained by direct separation by silica gel column chromatography (at a volume ratio of petroleum ether:ethyl acetate = 4:1). NMR analysis was performed, and the NMR data are as follows: 1H NMR (500MHz, CDCl3): δ7.14-7.08(m,3H),6.88(d,J=6.9Hz,1H),6.29(s,1H),3.32(s,1H),2.50(s,3H),2.46(s,9H),2.36(s,3H),2.30(s,3H). 13 C NMR (125MHz, CDCl3): δ195.0,161.0,156.1,147.3,137.7,129.0,128.2,125.43,125.36,122.2,104.6,52.7,37.7,29.3,21.7,14.6.

[0047] Example 5

[0048] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0049]

[0050] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3e (59.4 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1e (44.5 mg, yield 63%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.51 (s, 1H), 7.45-7.43 (m, 1H), 7.32 (d, J = 5.0Hz, 2H) ,6.33(s,1H),3.41(t,J=4.7Hz,1H),2.50(s,3H),2.51(s,9H),2.37(s,3H). 13 C NMR (125MHz, CDCl3): δ194.9, 159.8, 156.5, 148.5, 131.5, 130.3 (q, J = 31.3Hz), 128.6, 124.8, (q, J=3.8Hz), 124.6 (q, J=272.0Hz), 122.3, 121.8 (q, J=3.8Hz), 105.3, 52.7, 38.0, 29.3, 14.6.11 B NMR (160MHz, CDCl3): δ-1.5. 19 F NMR (471MHz, CDCl3): δ-62.30. High-resolution data: Calculated for [C 18 H 24 BF3NO2,M+H] + :354.1847,found:354.1855.

[0051] Example 6

[0052] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0053]

[0054] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3f (43.2 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1f (48.1 mg, 80% yield) is obtained by direct separation by silica gel column chromatography (at a volume ratio of petroleum ether:ethyl acetate = 4:1). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.31(d,J=7.6Hz,1H),7.08(t,J=7.3Hz,2H),6.97(t,J=7.5Hz ,1H),6.33(s,1H),3.55(s,1H),2.53(s,9H),2.51(s,3H),2.42(s,3H),2.36(s,3H). 13 C NMR (125MHz, CDCl3): δ194.9,161.1,156.1,145.2,134.1,130.2,128.1,126.0,124.4,122.3,105.4,52.8,32.7,29.3,20.4,14.7.

[0055] Example 7

[0056] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0057]

[0058] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), an acetylene aldehyde compound (54.0 mg, 0.3 mmol, 1.5 eq), and a borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55°C for 10 h. Finally, the α-furanborane compound is directly separated by silica gel column chromatography (at a volume ratio of petroleum ether:ethyl acetate = 4:1) to obtain 1 g (42.3 mg, yield 63%). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.79-7.71(m,3H),7.66(s,1H),7.52(d,J=8.4Hz,1H),7.40(t,J=6.7Hz,1H) ,7.35(t,J=7.2Hz,1H),6.35(s,1H),3.54(t,J=4.4Hz,1H),2.49(s,3H),2.48(s,9H),2.37(s,3H). 13 CNMR (125MHz, CDCl3): δ195.0,160.6,156.4,145.2,134.0,131.7,128.0,127 .8,127.7,127.4,125.7,125.6,124.7,122.2,105.0,52.8,38.0,29.3,14.6.

[0059] Example 8

[0060] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0061]

[0062] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3h (28.2 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55°C for 10 h. Finally, the α-furanborane compound 1h (39.8 mg, 80% yield) is directly separated by silica gel column chromatography (at a volume ratio of petroleum ether:ethyl acetate = 4:1) to obtain α-furanborane compound 1h. The NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ6.08(s,1H),2.52(s,3H),2.49(s,9H),2.35(s,3H),1.25(s ,1H),0.92-0.84(m,1H),0.52-0.46(m,1H),0.38-0.35(m,1H),0.13-0.03(m,2H). 13 C NMR (125MHz, CDCl3): δ195.1,163.5,155.5,122.2,102.9,52.5,34.7,29.2,16.0,14.6,6.5,5.2. 11 B NMR (160MHz, CDCl3): δ-1.8. High-resolution data: Calculated for [C 14 H 25 BNO2,M+H] + :250.1973,found:250.1977.

[0063] Example 9

[0064] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0065]

[0066] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3i (40.8 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1i (35.0 mg, 60% yield) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, v / v). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ6.14(s,1H),2.53(s,3H),2.43(s,9H),2.36(s,3H),1.76-1.63(m,6H),1.47-1.41(m,1H),1.21-0.86(m,5H). 13 C NMR (125MHz, CDCl3): δ195.3,163.1,155.5,122.2,105.1,52.5,43.0,35.7,33.4,31.7,29.3,27.3,27.2,26.9,14.7.

[0067] Example 10

[0068] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0069]

[0070] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3j (33.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1j (41.0 mg, yield 77%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1H NMR (500MHz, CDCl3): δ6.19 (s, 1H), 2.53 (s, 3H), 2.42 (s, 9H), 2.37 (s, 3H), 1.57 (d, J = 6.7Hz, 1H), 0.88 (s, 9H). 13 C NMR (125MHz, CDCl3): δ195.4,164.0,155.0,122.3,105.4,52.5,40.9,34.6,29.8,29.3,14.6.

[0071] Example 11

[0072] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0073]

[0074] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2b (25.6 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1k (31.4 mg, 50% yield) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.29(d,J=7.6Hz,2H),7.23(t,J=7.5Hz,2H),7.07(t,J=7.3Hz,1H),6.27(s,1H)3.38(t,J= 5.0Hz,1H),3.01-2.88(m,2H),2.70(q,J=7.2Hz,2H),2.47(s,9H),1.18(t,J=7.5Hz,3H),1.12(t,J=7.2Hz,3H),. 13 C NMR (125MHz, CDCl3): δ197.9,161.1,160.6,147.4,128.3,124.6,120.6,104.1,52.7,38.0,34.4,21.8,12.5,8.1.

[0075] Example 12

[0076] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0077]

[0078] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2c (23.2 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1l (54.4 mg, 90% yield) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.25(d,J=7.2Hz,2H),7.20(t,J=7.4Hz,2H),7.05(t,J=7.3 Hz,1H),6.33(s,1H),3.77(s,3H),3.34(t,J=4.6Hz,1H),2.49(s,3H),2.46(s,9H). 13 C NMR (125MHz, CDCl3): δ165.3,160.9,157.0,147.5,128.21,128.18,124.4,113.5,104.9,52.6,51.1,38.0,13.9.

[0079] Example 13

[0080] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0081]

[0082] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2d (37.6 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1m (45.7 mg, yield 63%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.97(d,J=7.1Hz,2H),7.39(t,J=7.3Hz,2H),7.35-7.30(m,3H),7.23(t,J =7.3Hz,2H),7.07(t,J=7.3Hz,1H),6.51(s,1H),3.79(s,3H),3.47(t,J=4.9Hz,1H),2.50(s,9H). 13 C NMR (125MHz, CDCl3): δ164.8,162.1,155.1,147.1,130.7,128.6,128.34,128.30,128.1,114.2,107.3,52.7,51.5,38.3. 11 B NMR (160MHz, CDCl3): δ-0.8. High-resolution data: Calculated for [C 22 H 27 BNO3, M+H] + :364.2079,found:364.2086.

[0083] Example 14

[0084] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0085]

[0086] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, a catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and a reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2e (39.6 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4a (58.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1n (41.5 mg, yield 54%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1 H NMR (500MHz, CDCl3): δ7.88 (d, J = 7.2Hz, 2H), 7.55-7.45 (m, 3H), 7.23-7.18 (m, 4H) ,7.07-7.04(m,1H),6.26(s,1H),3.30(t,J=4.5Hz,1H),2.48(s,3H),2.43(s,9H). 13 C NMR (125MHz, CDCl3): δ162.1,154.3,146.7,143.1,132.8,129.2,128.3,126.9,124.8,122.4,104.0,52.7,38.0,13.2.

[0087] Example 15

[0088] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0089]

[0090] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.2 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4b (79.2 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1o (44.2 mg, yield 71%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1H NMR (500MHz, CDCl3): δ7.29(d,J=7.6Hz,2H),7.22(t,J=7.5Hz,2H),7.07(t,J=7.3Hz,1H),6.29(s,1H),3.38(t,J=4.9Hz ,1H),3.15-3.09(m,1H),2.95-2.90(m,1H),2.72-2.68(m,1H),2.50(s,3H),2.46(s,3H),2.35(s,3H),2.00-1.80(m,5H). 13 C NMR (125MHz, CDCl3): δ195.0,161.1,156.1,147.6,128.24,128.22,124.5,122.1,104.5,62.0,61.6,47.6,37.9,29.2,22.4,22.1,14.6. 11 BNMR (160MHz, CDCl3): δ-2.6. High-resolution data: Calculated for [C 19 H 27 BNO2,M+H] + :312.2130,found:312.2138.

[0091] Example 16

[0092] A three-component strategy for synthesizing α-furanborane compounds, with the following reaction equation:

[0093]

[0094] A three-component strategy for synthesizing α-furanborane compounds is disclosed, with the following implementation: Under room temperature and air conditions, catalyst CuCl (2.0 mg, 0.02 mmol, 0.1 eq) and reaction solvent dichloromethane (0.5 mL) are added sequentially to a reaction vessel and stirred until homogeneous. Then, ketone compound 2a (20.0 mg, 0.2 mmol, 1.0 eq), acetylaldehyde compound 3a (39.0 mg, 0.3 mmol, 1.5 eq), and borane complex 4c (90.4 mg, 0.8 mmol, 4.0 eq) are added sequentially, and the reaction is carried out at 55 °C for 10 h. Finally, the α-furanborane compound 1p (48.1 mg, yield 74%) is obtained by direct separation by silica gel column chromatography (petroleum ether:ethyl acetate = 4:1, volume ratio). NMR analysis was performed, and the NMR data are as follows: 1H NMR (500MHz, CDCl3): δ7.28(d,J=7.3Hz,2H),7.22(t,J=7.4Hz,2H),7.06(t,J=7.2Hz,1H),6.29(s,1H),3.39(t,J=4.4Hz,1H),2.9 4-2.84(m,1H),2.86-2.80(m,1H),2.63-2.56(m,2H),2.50(s,3H),2.43(s,3H),2.35(s,3H),1.80-1.70(m,2H),1.61-1.43(m,4H). 13 C NMR (125MHz, CDCl3): δ195.0,161.2,156.1,147.9,128.21,128.19,124.4,122.2,104.5,59.0,58.9,46.3,37.1,29.3,22.7,20.3,20.2,14.6. 11 B NMR (160MHz, CDCl3): δ-2.4. High-resolution data: Calculated for [C 20 H 29 BNO2,M+H] + :326.2286,found:326.2292.

[0095] The embodiments described above are merely preferred technical solutions of the present invention and should not be considered as limitations on the present invention. The embodiments and features described in this application can be arbitrarily combined with each other without conflict. The scope of protection of the present invention should be limited to the technical solutions described in the claims, including equivalent substitutions of the technical features described in the claims. That is, equivalent substitutions and improvements within this scope are also within the scope of protection of the present invention.

Claims

1. A three-component strategy method for synthesizing α-furanborone compounds, characterized in that, The α -The structural formula of the furan borane compound is shown in formula (1): （1） Among them, R 1 It is an alkyl or aryl group; R 2 For COME, COEt, CO2Me, or SO2Ph; R 3 It is alkyl or aryl; LB is NMe3, or ; The three-component strategy synthesis method is as follows: using ketone compounds as shown in formula (2), acetylacetic aldehyde compounds as shown in formula (3), and borane compounds as shown in formula (4), under the catalysis of cuprous chloride as shown in formula (5), a one-step reaction is carried out to synthesize the compound shown in formula (1). α - Furanborane compounds; 。 2. The three-component strategy synthesis method for α-furanboron compounds according to claim 1, characterized in that, The specific steps include: adding the catalyst CuCl and the reaction solvent sequentially to a reaction vessel under room temperature and air conditions, and stirring until homogeneous; then adding ketone compounds, acetylene aldehyde compounds, and borane complexes sequentially for reaction; after the reaction is complete, separating by silica gel column chromatography to obtain... α - Furan borane compounds.

3. The three-component strategy synthesis method for α-furanboron compounds according to claim 2, characterized in that, The molar ratio of the ketone compound, acetylacetonate compound, borane complex and cuprous chloride is 1:1.5:4:0.

1.

4. The three-component strategy method for synthesizing α-furanboron compounds according to claim 1 or 2, characterized in that, The reaction solvent is dichloromethane, and 0.4 mmol of ketone compound is added to every 1.0 mL of reaction solvent.

5. The three-component strategy synthesis method for α-furanboron compounds according to claim 2, characterized in that, The reaction time is 10-20 hours.

6. The three-component strategy method for synthesizing α-furanboron compounds according to claim 5, characterized in that, The reaction was carried out at a temperature of 55°C.

7. The three-component strategy method for synthesizing α-furanboron compounds according to claim 2, characterized in that, After the reaction is complete, silica gel column chromatography is performed directly.

8. The three-component strategy synthesis method for α-furanboron compounds according to claim 2, characterized in that, When separating by silica gel column chromatography, the eluent is petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is 2:1 to 4:1.

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