1, 4-dihydrobenzo-silacyclohexane compound containing polyfunctional group structure as well as preparation method and application of 1, 4-dihydrobenzo-silacyclohexane compound

Abstract

The invention provides a 1, 4-dihydrobenzosilacyclohexane compound containing a polyfunctional group structure as well as a preparation method and application thereof, the preparation method specifically comprises the following steps: in the presence of a phosphine ligand, a palladium catalyst and a reaction medium, carrying out silicon-carbon bond activation and cycloaddition reaction on phenylpropargyl aldehyde and benzosilacyclobutane to prepare the 1, 4-dihydrobenzosilacyclohexane compound containing the polyfunctional group structure, and carrying out cycloaddition reaction on the 1, 4-dihydrobenzosilacyclohexane compound containing the polyfunctional group structure to obtain the 1, 4-dihydrobenzosilacyclohexane compound containing the polyfunctional group structure. The 2, 4-dihydrobenzo-silacyclohexane compound disclosed by the invention is applied to both material chemistry and medicinal chemistry. According to the present invention, the reaction condition is mild, the operation is simple, the substrate universality is strong, the crude product is subjected to rapid column chromatography impurity removal and vacuum concentration to obtain the pure product, the post-treatment is convenient, the finally obtained chemical selection is high, and the silicon-containing cyclohexane structure precursor can be widely used in various organic reactions and drug synthesis, and has considerable potential application value.

Description

Technical Field

[0001] The present invention relates to the field of organic chemistry, and particularly to a 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure, a preparation method thereof, and an application thereof. Background Art

[0002] Benzocyclosiloxane compounds are a class of organosilicon compounds with unique structures and functions, and have attracted much attention due to their potential application values shown in the fields of materials science, pharmaceutical chemistry, and organic synthesis. In the structure of such compounds, the introduction of silicon atoms not only enriches the chemical properties of the molecules, but also provides diverse possibilities for the functionalization of the molecules. However, there are many limitations in the traditional synthesis methods for preparing such compounds. For example, the synthesis efficiency is low, the reaction conditions are harsh, and it is difficult to obtain products with different substituents, which seriously restricts the wide application of benzocyclosiloxane compounds.

[0003] In previous studies, the synthesis of benzocyclosiloxane compounds usually relied on complex multi-step reaction processes, which often required harsh conditions such as high temperature and high pressure, and the reaction steps were cumbersome with low yields. In addition, it was difficult to precisely control the substituents of the products by traditional methods, resulting in a limited variety of synthesized compounds and unable to meet the requirements of different application scenarios for the structural diversity of compounds. For example, some synthesis methods require the use of specific reagents or complex protection and deprotection steps, which not only increase the synthesis cost, but also reduce the feasibility and scalability of the synthesis.

[0004] With the continuous development of organic synthetic chemistry, researchers have been exploring more efficient, mild, and universal synthesis methods in order to break through the limitations of traditional synthesis methods. Therefore, developing a new method that can efficiently, mildly, and controllably synthesize benzocyclosiloxane compounds with various different substituents has important scientific significance and practical application value. Summary of the Invention

[0005] The first object of the present invention is to provide a preparation method of a 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure in view of the deficiencies of the prior art. Two types of 1,4-dihydrobenzocyclosiloxane compounds containing a multi-functional group structure are synthesized by the cycloaddition silanization reaction of benzocyclosilacyclobutane and phenylpropiolaldehyde. The reaction method is simple and the conditions are mild, which can solve the problems such as low efficiency of the previous synthesis methods and difficulty in obtaining benzocyclosiloxane compounds with different substituents.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A preparation method of a 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure, comprising the following steps:

[0008] Under an inert gas atmosphere, a phosphine ligand, a metal catalyst, an additive, and a reaction medium are mixed. After stirring, a propargyl aldehyde compound 1 and a benzosilacyclobutane 2 are successively added and stirring is continued for the reaction. Then, methyllithium is added to obtain the 1,4-dihydrobenzosilacyclohexane compound 3 or 4 containing a multi-functional group structure;

[0009] The reaction route is as follows:

[0010]

[0011] Among them, R1 is one of hydrogen, alkyl, halogenated group, aryl, and alkoxy, R2 is hydrogen or methyl, and R3 is methyl or phenyl.

[0012] Preferably, the molar ratio of the propargyl aldehyde compound to the benzosilacyclobutane is 1:2 to 1:3.

[0013] Preferably, the concentration of the propargyl aldehyde compound is 0.1 mol / L. The propargyl aldehyde compound and the benzosilacyclobutane directly undergo a selective cycloaddition silane reaction under the action of a complex formed by a metal catalyst and a phosphine ligand. The reaction is easy to synthesize, the operation is simple, and the obtained crude product can be concentrated under reduced pressure after removing impurities by flash column chromatography, and the post-treatment is convenient.

[0014] Preferably, the reaction further includes post-treatment; the post-treatment is as follows: after the reaction is complete, the solvent is evaporated to obtain a crude product, and the crude product is separated and purified to obtain the 1,4-dihydrobenzosilacyclohexane compound containing a multi-functional group structure.

[0015] Preferably, the metal catalyst is bis(dibenzylideneacetone)palladium(0), and the usage amount is 3.5 - 6% of the molar amount of the propargyl aldehyde compound.

[0016] Preferably, the phosphine ligand is L1 or L2, and the usage amount is 10 - 12% of the molar amount of the propargyl aldehyde compound. In the present invention, a complex formed by a metal catalyst and a phosphine ligand is used as a catalyst precursor, and the catalytic efficiency is good, and a target product with a high yield can be obtained.

[0017]

[0018] Preferably, the reaction medium is selected from one or two of n-hexane, toluene, dichloromethane, and dichloroethane, and the usage amount is the amount that enables the solute to react fully; more preferably toluene.

[0019] Preferably, the reaction temperature is 10 - 40 °C, and the reaction time is 10 - 24 h.

[0020] The second objective of the present invention is to provide a 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure, which is prepared by the above method, and its structural formula is shown as follows:

[0021]

[0022] The third objective of the present invention is to provide the application of the above 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure in material chemistry or pharmaceutical chemistry. The silole structure it has is an important structural unit of luminescent materials.

[0023] Preferably, the above 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure can be widely used as a synthetic precursor in various organic reactions and pharmaceutical syntheses.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] The present invention prepares 1,4-dihydrobenzocyclosiloxane compounds through the selective Si-C(sp 3 ) bond cleavage of benzocyclosilacyclobutane by Pd-catalyzed and highly selective cycloaddition silylation. Using easily prepared asymmetric phenylpropiolaldehyde as the raw material and the complex formed by a metal catalyst palladium salt and a phosphine ligand as the catalyst precursor, the catalyst precursor participates in the catalytic cycle system with relatively high catalytic efficiency. The chemical selectivity of the product is controlled by additives, and the target product with extremely high yield can be obtained. A series of 1,4-dihydrobenzocyclosiloxane compounds are efficiently synthesized through intermolecular cycloaddition silylation reactions. The method of the present invention can complete the reaction by stirring at a relatively low temperature, with simple operation, high yield, and strong substrate universality. The crude product can be obtained as a pure product after impurity removal by flash column chromatography and concentration under reduced pressure. The post-treatment is convenient, and it is more direct and effective for synthesizing silacyclic compounds compared with the traditional chain silane cyclization reaction, and various benzocyclosiloxane compounds with different substituents that cannot be prepared by traditional methods can be obtained. Therefore, the present invention can be widely applied to the fields of material chemistry and pharmaceutical chemistry. Description of the Drawings

[0026] Figure 1 1H NMR spectrum of the 1,4-dihydrobenzocyclosiloxane compound prepared in Example 1;

[0027] Figure 2 13C NMR spectrum of the 1,4-dihydrobenzocyclosiloxane compound prepared in Example 1;

[0028] Figure 3 1H NMR spectrum of the 1,4-dihydrobenzocyclosiloxane compound prepared in Example 2;

[0029] Figure 41H NMR spectrum of the 1,4-dihydrobenzotrisilacyclohexane compound prepared in Example 2;

[0030] Figure 5 1H NMR spectrum of the 1,4-dihydrobenzotrisilacyclohexane compound prepared in Example 12;

[0031] Figure 6 13C NMR spectrum of the 1,4-dihydrobenzotrisilacyclohexane compound prepared in Example 12. Detailed implementation mode

[0032] The present invention will be further described in detail below with reference to examples. All raw materials used in the examples can be purchased commercially or prepared by conventional methods.

[0033] Example 1:

[0034] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent, pre-stir at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1a (0.20 mmol), stir for 15 min, then add benzotrisilacyclobutane (0.6 mmol), continue to stir and react at 30 °C for 20 h, directly add methyllithium, after monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 51 mg of a pale yellow oily liquid product 3a with a yield of 72%. Its 1H NMR spectrum is as shown in Figure 1 shown, and its 13C NMR spectrum is as shown in Figure 2 shown.

[0035]

[0036] The physical and chemical indexes of this product are as follows: 1 H NMR(400MHz,CDCl3)δ7.53–7.45(m,3H),7.32–7.23(m,6H),7.21–7.15(m,2H),7.12–7.06(m,3H),4.49(q,J=6.5Hz,1H),3.83(dd,J=92.8,21.2Hz,2H),1.76(b,1H),1.14(d,J=6.5Hz,3H),0.85(s,3H).

[0037] 1313C NMR (101 MHz, CDCl3) δ 149.3, 143.4, 143.0, 138.2, 137.1, 133.4, 132.8, 132.5, 128.0, 128.0, 127.4, 127.0, 126.8, 126.0, 125.8, 124.8, 69.8, 42.5, 23.1, -3.9. HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 24 NaOSi: 379.1489, found: 379.1489.

[0038] Example 2:

[0039] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (4.0 mg, 0.007 mmol) to a Schlenk reaction tube, then add 2.0 mL of n-hexane solvent. After pre-stirring at 10 °C for 10 min, add the phenylpropiolaldehyde compound 1c (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.4 mmol). Continue stirring the reaction at 30 °C for 24 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 44 mg of a pale yellow oily liquid product 3b with a yield of 59%. Its 1H NMR spectrum is as Figure 3 shown, and its 13C NMR spectrum is as Figure 4 shown.

[0040]

[0041] The physical and chemical indices of this product are: 1 1H NMR (400 MHz, CDCl3) δ 7.51–7.43 (m, 3H), 7.25–7.20 (m, 4H), 7.18–7.13 (m, 1H), 7.12–7.07 (m, 3H), 7.00–6.94 (m, 2H), 4.50 (q, J = 6.5 Hz, 1H), 3.81 (dd, J = 93.6, 21.2 Hz, 2H), 2.29 (s, 3H), 1.58 (b, 1H), 1.14 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0042] 1313C NMR (101 MHz, CDCl3) δ 149.3, 143.5, 140.1, 138.3, 137.0, 135.4, 133.4, 132.9, 132.5, 128.1, 128.0, 127.9, 127.0, 126.8, 125.9, 124.7, 69.8, 42.6, 23.1, 20.1, -3.9. HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 26 NaOSi: 393.1645, found: 393.1643.

[0043] Example 3:

[0044] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane and dichloromethane solvents. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1d (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 10 °C for 10 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 44 mg of a pale yellow oily liquid product 3c with a yield of 57%.

[0045]

[0046] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.51–7.44 (m, 3H), 7.26–7.20 (m, 4H), 7.18–7.14 (m, 1H), 7.09 (d, J = 7.6 Hz, 1H), 7.03–6.98 (m, 2H), 6.86–6.80 (m, 2H), 4.52 (q, J = 6.5 Hz, 1H), 3.81 (dd, J = 94.0, 21.2 Hz, 2H), 3.73 (s, 3H), 1.77 (b, 1H), 1.14 (d, J = 6.5 Hz, 3H), 0.83 (s, 3H).

[0047] 1313C NMR (101 MHz, CDCl3) δ 157.3, 149.0, 143.5, 138.2, 137.2, 135.3, 133.4, 132.9, 132.5, 128.0, 127.9, 127.2, 127.0, 126.7, 124.7, 112.8, 69.8, 54.2, 42.7, 23.1, -3.9. HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 26 NaO2Si: 409.1594, found: 409.1592.

[0048] Example 4:

[0049] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1e (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 40 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 38 mg of a pale yellow oily liquid product 3d with a yield of 51%.

[0050]

[0051] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.50–7.44 (m, 3H), 7.26–7.21 (m, 4H), 7.19–7.14 (m, 1H), 7.10 (d, J = 7.6 Hz, 1H), 7.07–7.01 (m, 2H), 7.01–6.95 (m, 2H), 4.46 (q, J = 6.5 Hz, 1H), 3.79 (dd, J = 96.8, 21.6 Hz, 2H), 1.49 (b, 1H), 1.13 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0052] 19 19F NMR (376 MHz, CDCl3) δ -115.50.

[0053] 1313C NMR (101 MHz, CDCl3) δ 160.6 (d, J = 245.6 Hz), 148.1, 143.2, 138.8 (d, J = 3.5 Hz), 138.0, 133.4, 132.7, 132.5, 128.1, 128.0, 127.7, 127.6, 127.0, 126.7, 124.8, 114.4 (d, J = 21.2 Hz), 69.7, 42.5, 23.1, -3.9.

[0054] HRMS (ESI) m / z: [M+Na] + calculated for C 247 H 23 NaFOSi: 397.1394, found: 397.1395.

[0055] Example 5:

[0056] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 20 °C for 10 min, add 1 g (0.20 mmol) of the phenylpropiolaldehyde compound. After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is complete, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 42 mg of the pale yellow oily liquid product 3e with a yield of 51%.

[0057]

[0058] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.51–7.44 (m, 3H), 7.32–7.27 (m, 2H), 7.25–7.20 (m, 4H), 7.18–7.13 (m, 1H), 7.09 (d, J = 7.6 Hz, 1H), 7.03–6.98 (m, 2H), 4.52 (q, J = 6.5 Hz, 1H), 3.83 (dd, J = 92.4, 21.2 Hz, 2H), 1.48 (b, 1H), 1.26 (s, 9H), 1.16 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0059] 1313C NMR (101 MHz, CDCl3) δ 149.4, 148.6, 143.6, 139.9, 138.2, 136.9, 133.4, 132.9, 132.5, 128.0, 127.9, 126.9, 126.7, 125.7, 124.7, 124.2, 69.7, 42.5, 33.5, 30.4, 23.2, -3.9.

[0060] HRMS (ESI) m / z: [M+Na] + calculated for C 28 H 32 NaOSi: 435.2115, found: 435.2111.

[0061] Example 6:

[0062] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1h (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 57 mg of a pale yellow oily liquid product 3f with a yield of 66%.

[0063]

[0064] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.56–7.46 (m, 7H), 7.37 (t, J = 7.6 Hz, 2H), 7.29–7.21 (m, 5H), 7.19–7.10 (m, 4H), 4.56 (q, J = 6.5 Hz, 1H), 3.86 (dd, J = 92.4, 21.2 Hz, 2H), 1.55 (b, 1H), 1.17 (d, J = 6.4 Hz, 3H), 0.86 (s, 3H).

[0065] 1313C NMR (101 MHz, CDCl3) δ 148.9, 143.4, 141.9, 139.6, 138.6, 138.1, 137.4, 133.4, 132.8, 132.8, 128.0, 128.0, 127.8, 127.0, 126.8, 126.5, 126.3, 126.1, 126.0, 124.8, 69.8, 42.4, 23.2, -3.9.

[0066] HRMS (ESI) m / z: [M+Na] + calculated for C 30 H 28 NaOSi: 455.1802, found: 455.1800.

[0067] Example 7:

[0068] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 40 °C for 10 min, add the phenylpropiolaldehyde compound 1m (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol), and continue to stir the reaction at 30 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3g, with a yield of 61%.

[0069]

[0070] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.51–7.44 (m, 3H), 7.26–7.20 (m, 4H), 7.20–7.13 (m, 2H), 7.09 (d, J = 7.6 Hz, 1H), 7.04–7.00 (m, 1H), 6.90–6.84 (m, 2H), 4.49 (q, J = 6.5 Hz, 1H), 3.81 (dd, J = 92.4, 21.6 Hz, 2H), 2.28 (s, 3H), 1.63 (b, 1H), 1.13 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0071] 1313C NMR (101 MHz, CDCl3) δ 149.5, 143.4, 143.0, 138.2, 137.1, 136.8, 133.4, 132.8, 132.5, 128.0, 127.9, 127.3, 127.0, 126.8, 126.6, 126.5, 124.7, 123.1, 69.8, 42.5, 23.1, 20.5, -3.9.

[0072] HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 26 NaOSi: 393.1645, found: 393.1643.

[0073] Example 8:

[0074] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 40 °C for 10 min, add the phenylpropiolaldehyde compound 1n (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 41 mg of a pale yellow oily liquid product 3h with a yield of 53%.

[0075]

[0076] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.51–7.44 (m, 3H), 7.28–7.20 (m, 5H), 7.18–7.14 (m, 1H), 7.09 (d, J = 7.6 Hz, 1H), 6.74 (s, 1H), 6.68–6.59 (m, 2H), 4.51 (q, J = 6.5 Hz, 1H), 3.98–3.66 (m, 2H), 3.72 (s, 3H), 1.56 (b, 1H), 1.15 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0077] 1313C NMR (101 MHz, CDCl3) δ 158.5, 149.0, 144.4, 143.3, 138.1, 137.1, 133.4, 132.8, 132.5, 128.5, 127.98, 127.95, 127.0, 126.8, 124.8, 118.4, 111.9, 110.9, 69.7, 54.2, 42.3, 23.2, -3.9.

[0078] HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 26 NaO2Si: 409.1594, found: 409.1587.

[0079] Example 9:

[0080] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of dichloromethane solvent. After pre-stirring at 30 °C for 10 min, add 1 g (0.20 mmol) of phenylpropiolaldehyde compound. After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 24 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3i with a yield of 61%.

[0081]

[0082] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.54–7.47 (m, 4H), 7.45–7.42 (m, 1H), 7.26–7.19 (m, 7H), 7.17–7.08 (m, 9H), 7.02–6.98 (m, 1H), 6.94–6.90 (m, 1H), 4.48 (q, J = 6.5 Hz, 1H), 4.20 (q, J = 6.4 Hz, 1H), 3.75 (dd, J = 82.8, 22.0 Hz, 2H), 3.66 (dd, J = 90.8, 21.2 Hz, 2H), 2.17 (s, 3H), 2.09 (s, 2H), 1.51 (b, 2H), 1.07 (d, J = 6.5 Hz, 3H), 1.01 (d, J = 6.4 Hz, 2H), 0.84 (s, 5H).

[0083] 1313C NMR (101 MHz, CDCl3) δ 149.9, 148.3, 143.5, 143.1, 142.1, 142.0, 138.4, 138.0, 133.4, 133.3, 133.3, 133.2, 132.6, 132.6, 132.4, 132.0, 129.4, 129.2, 128.0, 128.0, 127.9, 127.0, 126.9, 126.8, 126.8, 126.6, 126.1, 126.0, 125.9, 124.99, 124.95, 124.8, 70.3, 69.5, 22.8, 21.9, 18.3, 18.3, -3.8, -4.0

[0084] HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 26 NaOSi: 393.1645, found: 393.1642.

[0085] Example 10:

[0086] Under a nitrogen atmosphere, add the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube, then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1o (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. Directly add methyllithium. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 45 mg of a pale yellow oily liquid product 3j with a yield of 59%.

[0087]

[0088] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.52–7.43 (m, 3H), 7.27–7.19 (m, 4H), 7.17–7.07 (m, 2H), 6.84 (s, 1H), 6.68 (s, 2H), 4.50 (q, J = 6.5 Hz, 1H), 3.80 (dd, J = 90.8, 21.6 Hz, 2H), 2.24 (s, 6H), 1.58 (b, 1H), 1.14 (d, J = 6.5 Hz, 3H), 0.84 (s, 3H).

[0089] 1313C NMR (101 MHz, CDCl3) δ 149.7, 143.5, 143.0, 138.3, 136.9, 136.5, 133.4, 132.8, 132.5, 127.9, 127.9, 127.3, 126.9, 126.7, 124.7, 123.7, 69.8, 42.5, 23.1, 20.3, -3.9. HRMS (ESI) m / z: [M+Na] + calculated for C 26 H 28 NaOSi: 407.1802, found: 407.1804.

[0090] Example 11:

[0091] Under a nitrogen atmosphere, the phosphine ligand L1 (10.2 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube, and then 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1q (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. Methyllithium was directly added. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 50 mg of a pale yellow oily liquid product 3k with a yield of 62%.

[0092]

[0093] The physical and chemical indexes of this product: 1 1H NMR (400 MHz, CDCl3) δ 7.80–7.71 (m, 3H), 7.56–7.46 (m, 4H), 7.43–7.37 (m, 2H), 7.27–7.20 (m, 5H), 7.19–7.15 (m, 1H), 7.11 (t, J = 8.0 Hz, 1H), 4.54 (q, J = 6.5 Hz, 1H), 3.90 (dd, J = 89.7, 21.3 Hz, 2H), 1.55 (b, 1H), 1.14 (d, J = 6.6 Hz, 3H), 0.87 (s, 3H).

[0094] 1313C NMR (101 MHz, CDCl3) δ 149.1, 143.4, 140.4, 138.1, 137.6, 133.4, 132.8, 132.6, 132.3, 131.1, 128.0, 128.0, 127.2, 127.0, 126.8, 126.8, 126.7, 125.3, 124.9, 124.8, 124.8, 124.4, 69.8, 42.5, 23.2, -3.9.

[0095] HRMS (ESI) m / z: [M+Na] + calculated for C 28 H 26 NaOSi: 429.1645, found: 429.1643.

[0096] Example 12:

[0097] Under a nitrogen atmosphere, add the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of n-hexane and dichloroethane solvents. After pre-stirring at 30 °C for 20 min, add the phenylpropiolaldehyde compound 1a (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 10 °C for 10 h. After monitoring the reaction by TLC until it is completed, then filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 60 mg of a pale yellow oily liquid product 4a with a yield of 88%. Its 1H NMR spectrum is as Figure 5 shown, and its 13C NMR spectrum is as Figure 6 shown.

[0098]

[0099] The physical and chemical indexes of this product are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.55 (s, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.37–7.26 (m, 5H), 7.25–7.15 (m, 6H), 6.99–6.83 (m, 2H), 3.94 (dd, J = 170.7, 21.1 Hz, 2H), 0.48 (s, 3H).

[0100] 1313C NMR (100 MHz, CDCl3) δ 190.8, 157.7, 146.0, 143.0, 137.1, 133.7, 133.5, 132.9, 130.1, 128.88, 128.85, 127.8, 127.2, 127.1, 127.0, 126.1, 125.1, 31.3, -6.4.

[0101] HRMS (ESI) m / z: [M+Na] + calculated for C 23 H 20 NaOSi: 363.1176, found: 363.1175.

[0102] Example 13:

[0103] Under a nitrogen atmosphere, add the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of dichloroethane solvent. After pre-stirring at 30 °C for 20 min, add the phenylpropiolaldehyde compound 1b (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is complete, filter, extract, concentrate the filtrate, and purify by silica gel column chromatography to obtain 71 mg of a pale yellow oily liquid product 4b with a yield of 88%.

[0104]

[0105] The physical and chemical indices of this product: 1 1H NMR (400 MHz, CDCl3) δ 9.59 (s, 1H), 7.44–7.39 (m, 1H), 7.39–7.35 (m, 4H), 7.34–7.26 (m, 4H), 7.23–7.16 (m, 5H), 7.09–7.03 (m, 3H), 6.87–6.82 (m, 2H), 3.95 (s, 2H).

[0106] 13 13C NMR (101 MHz, CDCl3) δ 190.9, 156.2, 147.2, 143.5, 136.8, 135.1, 134.1, 130.7, 129.1, 129.0, 128.9, 127.84, 127.77, 127.0, 126.9, 126.2, 125.0, 31.4.

[0107] HRMS (ESI) m / z: [M+H] +calculated for C 28 H 23 OSi:403.1513,found:403.1507.

[0108] Example 14:

[0109] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube, and then 2.0 mL of dichloroethane solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1c (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 24 h. After the reaction was monitored by TLC and completed, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 50 mg of a pale yellow oily liquid product 4c with a yield of 71%.

[0110]

[0111] The physical and chemical indexes of this product: 1 H NMR(400MHz,CDCl3)δ9.56(s,1H),7.46(d,J=7.3Hz,1H),7.36–7.26(m,5H),7.25–7.17(m,3H),7.02(d,J=7.7Hz,2H),6.81(d,J=7.6Hz,2H),3.93(dd,J=180.8,21.0Hz,2H),2.26(s,3H),0.49(s,3H).

[0112] 13 C NMR(100MHz,CDCl3)δ190.9,157.7,146.1,143.1,136.0,134.0,133.7,133.7,132.8,130.3,128.8,128.8,127.9,127.8,127.1,127.1,125.1,31.4,20.1,-6.4.HRMS(ESI)m / z:[M+Na] + calculated for C 24 H 22 NaOSi:377.1332,found:377.1331.

[0113] Example 15:

[0114] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1d (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 55 mg of the product 4d as a pale yellow oily liquid, with a yield of 74%.

[0115]

[0116] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.58 (s, 1H), 7.45 (d, J = 7.3 Hz, 1H), 7.35–7.29 (m, 4H), 7.29–7.25 (m, 1H), 7.25–7.16 (m, 3H), 6.86 (d, J = 8.2 Hz, 2H), 6.75 (d, J = 8.2 Hz, 2H), 3.93 (dd, J = 179.9, 21.1 Hz, 2H), 3.71 (s, 3H), 0.49 (s, 3H).

[0117] 13 C NMR (100 MHz, CDCl3) δ 190.9, 158.0, 157.1, 146.1, 143.1, 133.8, 133.6, 132.8, 130.4, 129.2, 128.8, 128.6, 127.8, 127.1, 125.0, 112.7, 54.2, 31.5, -6.3.

[0118] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 22 NaO2Si: 393.1281, found: 393.1282.

[0119] Example 16:

[0120] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1e (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated. The product was purified by silica gel column chromatography to obtain 63 mg of a pale yellow oily liquid product 4e with a yield of 88%.

[0121]

[0122] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.55 (s, 1H), 7.49–7.44 (m, 1H), 7.36–7.33 (m, 2H), 7.32–7.28 (m, 3H), 7.27–7.19 (m, 3H), 6.96–6.83 (m, 4H), 3.95 (dd, J = 153.4, 21.2 Hz, 2H), 0.49 (s, 3H).

[0123] 19 F NMR (376 MHz, CDCl3) δ -114.92.

[0124] 13 C NMR (100 MHz, CDCl3) δ 190.4, 161.0 (d, J = 247.0 Hz), 156.5, 146.5, 142.9, 133.7, 133.3, 132.9, 132.9, 129.8, 129.0, 128.7, 128.6, 127.8, 127.1, 125.2, 114.3 (d, J = 21.5 Hz), 31.4, -6.4.

[0125] HRMS (ESI) m / z: [M+Na] + calculated for C 23 H 19 NaFOSi: 381.1081, found: 381.1080.

[0126] Example 17:

[0127] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of dichloroethane solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1f (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After the reaction was monitored by TLC and completed, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 42 mg of a pale yellow oily liquid product 4f with a yield of 56%.

[0128]

[0129] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.53 (d, J = 1.2 Hz, 1H), 7.50–7.41 (m, 1H), 7.36–7.26 (m, 5H), 7.26–7.17 (m, 5H), 6.83 (d, J = 7.9 Hz, 2H), 3.94 (dd, J = 154.1, 21.3 Hz, 2H), 0.48 (d, J = 1.2 Hz, 3H).

[0130] 13 C NMR (101 MHz, CDCl3) δ 191.4, 157.4, 147.5, 143.9, 136.7, 134.7, 134.2, 134.0, 133.3, 130.7, 130.1, 130.1, 129.4, 128.9, 128.5, 128.2, 126.3, 32.4, -5.4.

[0131] HRMS (ESI) m / z: [M+Na] + calculated for C 23 H 19 NaClOSi: 397.0786, found: 397.0784.

[0132] Example 18:

[0133] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, 1 g (0.20 mmol) of phenylpropiolaldehyde compound was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 55 mg of a pale yellow oily liquid product 4g, with a yield of 69%.

[0134]

[0135] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.56 (s, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.35–7.29 (m, 4H), 7.29–7.25 (m, 1H), 7.25–7.16 (m, 2H), 6.86 (d, J = 7.9 Hz, 2H), 3.93 (dd, J = 196.8, 21.0 Hz, 2H), 1.22 (s, 9H), 0.49 (s, 3H).

[0136] 13 C NMR (100 MHz, CDCl3) δ 191.0, 157.7, 149.2, 146.1, 143.1, 134.0, 133.8, 133.6, 132.8, 130.5, 128.8, 128.8, 127.8, 127.1, 127.0, 125.1, 124.0, 33.5, 31.4, 30.3, -6.3. HRMS (ESI) m / z: [M+Na] + calculated for C 27 H 28 NaOSi: 419.1802, found: 419.1798.

[0137] Example 19:

[0138] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1h (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 70 mg of the product 4h as a pale yellow oily liquid, with a yield of 84%.

[0139]

[0140] The physical and chemical indicators of this product are as follows: 1 HNMR (400 MHz, CDCl3) δ 9.62 (s, 1H), 7.53–7.41 (m, 5H), 7.37–7.30 (m, 6H), 7.28–7.17 (m, 5H), 6.98 (d, J = 7.7 Hz, 2H), 3.96 (dd, J = 174.9, 21.1 Hz, 2H), 0.52 (s, 3H).

[0141] 13 C NMR (100 MHz, CDCl3) δ 190.7, 157.2, 146.2, 143.0, 139.2, 138.9, 136.1, 133.7, 133.5, 132.9, 130.1, 128.9, 127.8, 127.8, 127.6, 127.1, 126.4, 125.9, 125.8, 125.1, 31.4, -6.3.

[0142] HRMS (ESI) m / z: [M+Na] + calculated for C 29 H 24 NaOSi: 439.1489, found: 439.1488.

[0143] Example 20:

[0144] Under a nitrogen atmosphere, phosphine ligand L2 (22 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1i (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 50 mg of a pale yellow oily liquid product 4i with a yield of 61%.

[0145]

[0146] The physical and chemical indexes of this product are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.48 (s, 1H), 7.50–7.44 (m, 3H), 7.36–7.33 (m, 2H), 7.31–7.20 (m, 6H), 7.00 (d, J = 7.9 Hz, 2H), 3.96 (dd, J = 149.9, 21.3 Hz, 2H), 0.48 (s, 3H).

[0147] 19 19F NMR (376 MHz, CDCl3) δ -62.44.

[0148] 13 13C NMR (101 MHz, CDCl3) δ 191.1, 157.4, 147.5, 143.8, 142.3, 134.7, 134.1, 134.0, 130.4, 130.2, 130.2, 129.4 (q, J = 32.5 Hz), 129.0, 128.3, 128.2, 126.4, 125.3 (q, J = 3.7 Hz), 122.7 (q, J = 270.1 Hz), 32.3, -5.5.

[0149] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 19 NaF3OSi: 431.1049, found: 431.1051.

[0150] Example 21:

[0151] Under a nitrogen atmosphere, phosphine ligand L2 (22 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1j (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated. The product was purified by silica gel column chromatography to obtain 72 mg of a pale yellow oily liquid product 4j with a yield of 90%.

[0152]

[0153] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.49 (s, 1H), 7.88 (d, J = 8.4 Hz, 2H), 7.53–7.42 (m, 1H), 7.34–7.18 (m, 8H), 6.97 (t, J = 7.5 Hz, 2H), 3.95 (dd, J = 143.1, 21.2 Hz, 2H), 3.81 (s, 3H), 0.47 (s, 3H).

[0154] 13 C NMR (101 MHz, CDCl3) δ 190.1, 165.7, 156.8, 146.1, 142.8, 142.4, 133.7, 133.0, 132.9, 129.5, 129.1, 128.5, 127.9, 127.8, 127.2, 126.9, 125.2, 51.1, 31.2, -6.5. HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 22 NaO3Si: 421.1230, found: 421.1231.

[0155] Example 22:

[0156] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1k (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 56 mg of the product 4k as a pale yellow oily liquid, with a yield of 79%.

[0157]

[0158] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.55 (s, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.35–7.25 (m, 5H), 7.24–7.16 (m, 3H), 7.12–7.04 (m, 1H), 7.02–6.95 (m, 1H), 6.77–6.63 (m, 2H), 3.93 (dd, J = 174.5, 21.1 Hz, 2H), 2.19 (s, 3H), 0.48 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 190.9, 157.9, 145.9, 143.1, 137.0, 136.8, 133.7, 133.6, 132.9, 130.2, 128.8, 128.8, 127.8, 127.8, 127.0, 126.8, 125.1, 124.1, 31.3, 20.4, -6.4. HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 22 NaOSi: 377.1332, found: 377.1331.

[0159] Example 23:

[0160] Under a nitrogen atmosphere, add the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of dichloromethane solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1l (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 30 °C for 20 h. After monitoring the reaction by TLC until it is completed, filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 52 mg of a pale yellow oily liquid product 4l with a yield of 70%.

[0161]

[0162] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.57 (s, 1H), 7.45 (d, J = 7.3 Hz, 1H), 7.36–7.25 (m, 5H), 7.25–7.17 (m, 3H), 7.15–7.08 (m, 1H), 6.76–6.69 (m, 1H), 6.50 (d, J = 7.5 Hz, 1H), 6.38 (s, 1H), 3.94 (dd, J = 160.2, 21.2 Hz, 2H), 3.57 (s, 3H), 0.49 (s, 3H).

[0163] 13 C NMR (100 MHz, CDCl3) δ 190.9, 158.2, 157.4, 145.9, 143.0, 138.5, 133.7, 133.6, 132.9, 130.0, 128.9, 128.9, 128.2, 127.8, 127.1, 125.1, 119.6, 112.1, 112.0, 54.0, 31.3, -6.4.

[0164] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 22 NaO2Si: 393.1281, found: 393.1283.

[0165] Example 24:

[0166] Under a nitrogen atmosphere, phosphine ligand L2 (22 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1m (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 20 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated. The residue was purified by silica gel column chromatography to obtain 54 mg of a pale yellow oily liquid product 4m with a yield of 76%.

[0167]

[0168] The physical and chemical indices of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.40 (s, 1H), 9.38 (s, 1H), 7.52–7.42 (m, 2H), 7.39–7.32 (m, 4H), 7.30–7.18 (m, 8H), 7.16–7.03 (m, 8H), 6.99–6.90 (m, 3H), 6.53 (dd, J = 7.6, 1.4 Hz, 1H), 3.97 (dd, J = 63.2, 21.2 Hz, 2H), 3.94 (dd, J = 185.1, 21.1 Hz, 2H), 2.03 (s, 3H), 1.48 (s, 3H), 0.52 (s, 3H), 0.42 (s, 3H).

[0169] 13 C NMR (101 MHz, CDCl3) δ 191.1, 190.9, 158.5, 158.5, 145.5, 145.0, 143.2, 143.1, 136.2, 136.0, 133.9, 133.8, 133.7, 133.5, 133.2, 133.1, 132.8, 129.9, 129.1, 129.1, 129.0, 128.91, 128.86, 128.8, 128.0, 127.9, 127.0, 126.9, 126.52, 126.48, 125.84, 125.80, 125.10, 125.05, 124.5, 124.4, 30.9, 30.9, 19.7, 18.8, -5.7, -7.1.

[0170] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 22 NaOSi: 377.1332, found: 377.1329.

[0171] Example 25:

[0172] Under a nitrogen atmosphere, phosphine ligand L2 (22 mg, 0.02 mmol) and metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube, and then 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, propargyl aldehyde compound 1n (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 10 °C for 22 h. After the reaction was monitored by TLC and completed, it was filtered, extracted, the filtrate was concentrated, and purified by silica gel column chromatography to obtain 63 mg of a pale yellow oily liquid product 4n with a yield of 85%.

[0173]

[0174] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.59 (s, 1H), 9.55 (s, 1H), 7.50 (d, J = 7.2 Hz, 1H), 7.41–7.23 (m, 7H), 7.22–7.07 (m, 12H), 6.91–6.80 (m, 2H), 6.75–6.61 (m, 4H), 3.93 (dd, J = 70.4, 20.4 Hz, 2H), 3.89 (dd, J = 254.8, 20.2 Hz, 2H), 3.52 (s, 3H), 3.25 (s, 3H), 0.52 (s, 3H), 0.41 (s, 3H).

[0175] 13 C NMR (101 MHz, CDCl3) δ 190.8, 190.7, 156.0, 155.6, 155.0, 154.8, 146.8, 146.2, 143.5, 143.4, 134.4, 133.6, 133.3, 132.9, 132.3, 132.0, 129.8, 129.5, 128.5, 128.4, 128.24, 128.16, 127.9, 127.6, 127.5, 126.6, 126.6, 125.8, 125.6, 124.9, 124.8, 119.2, 119.2, 109.12, 109.09, 53.9, 53.3, 31.2, 31.0, -6.4, -7.0.

[0176] HRMS (ESI) m / z: [M+Na] + calculated for C 24 H 22NaO2Si: 393.1281, found: 393.1281.

[0177] Example 26:

[0178] Under a nitrogen atmosphere, add the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the phenylpropiolaldehyde compound 1o (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 10 °C for 20 h. After monitoring the reaction by TLC until it is completed, filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 55 mg of a pale yellow oily liquid product 4o with a yield of 75%.

[0179]

[0180] The physical and chemical indexes of this product: 1 H NMR (400 MHz, CDCl3) δ 9.56 (s, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.34–7.25 (m, 5H), 7.23–7.16 (m, 3H), 6.80 (s, 1H), 6.50 (s, 2H), 3.91 (dd, J = 177.4, 21.0 Hz, 2H), 2.14 (s, 6H), 0.47 (s, 3H).

[0181] 13 C NMR (100 MHz, CDCl3) δ 191.0, 158.0, 145.8, 143.2, 136.9, 136.6, 133.7, 132.9, 130.3, 128.8, 128.8, 127.8, 127.7, 127.0, 125.02, 124.98, 31.3, 20.2, -6.4.

[0182] HRMS (ESI) m / z: [M+Na] + calculated for C 25 H 24 NaOSi: 391.1489, found: 391.1483.

[0183] Example 27:

[0184] Under a nitrogen atmosphere, add the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (3.0 mg, 0.006 mmol) to a Schlenk reaction tube. Then add 2.0 mL of toluene solvent. After pre-stirring at 30 °C for 10 min, add the propargyl aldehyde compound 1p (0.20 mmol). After stirring for 15 min, add benzosilacyclobutane (0.6 mmol). Continue stirring the reaction at 20 °C for 24 h. After monitoring the reaction by TLC until it is completed, filter, extract, concentrate the filtrate, and purify it by silica gel column chromatography to obtain 61 mg of a pale yellow oily liquid product 4p with a yield of 81%.

[0185]

[0186] The physical and chemical indexes of this product are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.55 (s, 1H), 7.45 (d, J = 7.3 Hz, 1H), 7.39–7.20 (m, 8H), 6.69–6.61 (m, 1H), 6.43 (s, 2H), 3.94 (dd, J = 138.8, 21.3 Hz, 2H), 0.52 (s, 3H).

[0187] 19 F NMR (376 MHz, CDCl3) δ -108.99.

[0188] 13 C NMR (101 MHz, CDCl3) δ 189.9, 161.7 (d, J = 250.7 Hz), 161.6 (d, J = 250.9 Hz), 155.3, 146.6, 142.6, 140.8, 133.6, 133.0, 132.7, 129.2, 129.2 (d, J = 9.0 Hz), 127.9, 127.3, 125.3, 110.0 (d, J = 25.5 Hz), 101.5 (t, J = 25.2 Hz), 31.2, -6.5. HRMS (ESI) m / z: [M+Na] + calculated for C 23 H 18 NaF2OSi: 399.0987, found: 399.0987.

[0189] Example 28:

[0190] Under a nitrogen atmosphere, the phosphine ligand L2 (22 mg, 0.02 mmol) and the metal catalyst bis(dibenzylideneacetone)palladium (5.7 mg, 0.01 mmol) were added to a Schlenk reaction tube. Then, 2.0 mL of toluene solvent was added. After pre-stirring at 30 °C for 10 min, the propargyl aldehyde compound 1q (0.20 mmol) was added. After stirring for 15 min, benzosilacyclobutane (0.6 mmol) was added, and the reaction was continued to stir at 30 °C for 20 h. After monitoring the reaction by TLC until completion, the mixture was filtered, extracted, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 56 mg of the product 4q as a pale yellow oily liquid with a yield of 71%.

[0191]

[0192] The physical and chemical indices of this product are as follows: 1 HNMR (400 MHz, CDCl3) δ 9.57 (s, 1H), 7.81–7.58 (m, 3H), 7.50–7.43 (m, 1H), 7.41–7.26 (m, 8H), 7.25–7.17 (m, 3H), 7.05 (d, J = 8.5 Hz, 1H), 3.99 (dd, J = 175.5, 21.1 Hz, 2H), 0.48 (s, 3H).

[0193] 13 C NMR (101 MHz, CDCl3) δ 191.8, 158.8, 147. / 5, 144.2, 135.9, 134.8, 134.7, 134.0, 133.0, 132.4, 131.2, 130.0, 130.0, 129.0, 128.2, 128.0, 127.9, 127.8, 127.1, 126.7, 126.3, 126.2, 32.6, -5.2.

[0194] HRMS (ESI) m / z: [M+Na] + calculated for C 27 H 22 NaOSi: 413.1332, found: 413.1330.

[0195] In summary, the above are only the preferred embodiments of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope covered by the patent of the present invention.

Claims

1. A preparation method of a 1,4-dihydrobenzocyclosiloxane compound containing a multi-functional group structure, characterized in that, The preparation method comprises the following steps: Under an inert gas atmosphere, a phosphine ligand, a metal catalyst, an additive, and a reaction medium are mixed. After stirring, a propargyl aldehyde compound 1 and a benzosilacyclobutane 2 are successively added and stirring is continued for the reaction. Then, sodium borohydride is added for reduction to obtain the 1,4-dihydrobenzosilacyclohexane compound 3 or 4 containing a multi-functional group structure; The reaction route is as follows: Among them, R1 is one of hydrogen, alkyl, halogenated group, aryl, and alkoxy group, R2 is hydrogen or methyl, and R3 is methyl or phenyl.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the propargyl aldehyde compound 1 to the benzosilacyclobutane 2 is 1:2 to 1:

3.

3. The preparation method according to claim 2, characterized in that, The concentration of the propargyl aldehyde compound 1 is 0.1 mol / L.

4. The preparation method according to claim 1, wherein, The preparation method further comprises post-treatment; the post-treatment is: after the reaction is complete, the solvent is evaporated to obtain a crude product, and the crude product is separated and purified to obtain the 1,4-dihydrobenzosilacyclohexane compound 3 or 4 containing a multi-functional group structure.

5. The preparation method according to claim 1, characterized in that, The metal catalyst is bis(dibenzylideneacetone)palladium(0), and the usage amount is 3.5 - 6% of the molar amount of the propargyl aldehyde compound 1.

6. The preparation method according to claim 1, characterized in that, The phosphine ligand is L1 or L2: The usage amount is 10 - 12% of the molar amount of the propargyl aldehyde compound.

7. The preparation method according to claim 1, wherein, The reaction medium is selected from one or two of n-hexane, toluene, dichloromethane, and dichloroethane.

8. The preparation method according to claim 1, wherein, The reaction temperature is 10 - 40 °C, and the reaction time is 10 - 24 h.

9. A 1,4-dihydrobenzosilacyclohexane compound containing a multi-functional group structure, which is prepared by the method according to any one of claims 1 - 7.

10. Use of the 1,4-dihydrobenzosilacyclohexane compound containing a multi-functional group structure according to claim 9 in materials chemistry or pharmaceutical chemistry.

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