Preparation method of eight-membered aryl silicon heterocycle and alkenyl silicon heterocyclic compound

Abstract

The invention provides a method for synthesizing an eight-membered aryl silicon heterocycle and alkenyl silicon heterocyclic compound based on palladium-catalyzed olefin C (sp2)-H activation / ring expansion cascade reaction. According to the method, simple and easily available o-halogen styrene derivatives and silacyclobutane are taken as initial raw materials, under the action of a palladium catalyst, a phosphine ligand, an additive and alkali, stirring reaction is performed in an organic solvent at the temperature of 30-100 DEG C, and the eight-membered aryl silicon heterocycle or alkenyl silicon heterocyclic compound can be obtained. The method has the advantages of cheap and easily available raw materials, mild reaction conditions, simple preparation process, good regioselectivity, high synthesis efficiency, wide substrate application range, easy amplification and the like. The method disclosed by the invention is an important supplement for synthesizing the silicon-impurity eight-membered ring compound in the prior art, and has a relatively high application value.

Description

Technical Field

[0001] The invention relates to a preparation method of an octa-membered aryl silicon heterocycle and an alkenyl silicon heterocycle compound, and belongs to the field of organic synthesis. Background Art

[0002] Benzo-8-membered ring building blocks are widely found in active natural products and pharmaceutical molecules. Because silicon is a bioisostere of carbon, replacing one carbon atom or heteroatom in these building blocks with a silicon atom through a "silicon substitution" strategy is of great significance for studying their new activities. However, the synthesis of benzo-8-silicon heterocyclic compounds is challenging due to factors such as unfavorable enthalpy and entropy effects, cross-ring interactions, and the properties of silicon. At present, the developed synthesis methods are mainly synthesized by the σ-bond cross-interchange reaction of silacyclobutane with another strained four-membered ring ([1] J. Am. Chem. Soc. 2014, 136, 5912; [2] J. Am. Chem. Soc. 2017, 139, 12414; [3] CCS Chem. 2023, 5, 1753); [4] J. Organomet. Chem. 2015, 797, 57; [5] Angew. Chem. Int. Ed., 2024, 63, e202319187). Although this method has 100% atom economy, it requires two strained four-membered rings as substrates, which greatly limits the universality of the reaction and the diversity of the products. Therefore, the development of simple and efficient new synthetic methods to use simple and readily available raw materials to construct structurally diverse medium-ring benzosilacyclohexane octahedral compounds remains a research hotspot and difficulty in the field of organic synthetic chemistry. Summary of the Invention

[0003] To address the shortcomings of the prior art, the present invention provides a method for preparing eight-membered arylsilyl heterocycles and alkenylsilyl heterocycles. This method utilizes readily available and inexpensive raw materials, employs mild reaction conditions, and features a simple preparation process, excellent regioselectivity, a wide range of substrate applicability, and scalability to gram quantities.

[0004] The technical solutions provided by the present invention are as follows:

[0005] A method for preparing a benzosilane 8-membered ring compound as shown in I (8-membered arylsilane ring) or II (8-membered alkenylsilane ring), comprising the following steps:

[0006] Under a protective gas atmosphere, an o-halostyrene derivative A and a silacyclobutane B are used as starting materials, and in the presence of a palladium catalyst C, a phosphine ligand D, a base E, and an additive F, the reaction is stirred in an organic solvent G at 30° C. to 100° C. for 1 to 40 hours. After the reaction, the reaction mixture is filtered, extracted, concentrated, and purified by column chromatography to obtain a benzosilacyclopentane octane compound represented by Formula I or II. The reaction equation is as follows:

[0007]

[0008] in:

[0009] X is iodine or bromine, R 1 -R 5 is one or more of aryl, heteroaryl, alkyl, ester, aldehyde, carbonyl, carboxyl, hydroxyl, mercapto, silyl, amino, cyano, nitro, amide, sulfonyl, alkoxy, alkenyl, alkynyl, halogen, and hydrogen; n represents R 1 The number of groups is 0≤n≤4. When n≥2, the two groups may be the same or different. Ar is an aromatic hydrocarbon or a heterocyclic aromatic hydrocarbon.

[0010] Furthermore, the protective gas is selected from one of argon and nitrogen, and argon is preferred in the present invention.

[0011] Furthermore, the palladium catalyst is any one or more of Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd(OAc)2, Pd(acac)2, Pd(TFA)2, Pd(OAc)2(PPh3)2, PdCl2(dppf)·DCM, Pd(cod)2Cl2, Pd(PPh3)2Cl2, Pd(MeCN)2Cl2, PdCl2, PdI2, [Pd(allyl)Cl]2, and [Pd(PhC3H4)Cl]2, and Pd(TFA)2 is preferred in the present invention.

[0012] Furthermore, the phosphine ligand is triarylphosphine, trialkylphosphine, dppm, dppe, dppp, dppb, dppf, BINAP, DPEPhos, AmPhos, DavePhos, BrettPhos, MePhos, XPhos, SPhos, AmPhos, RuPhos, XantPhos, t Bu-DavePhos, t Bu-BrettPhos, t Bu-XPhos、Me4 t Bu-Xphos, t Any one or more of Bu-MePhos and JohnPhos. tBu-MePhos.

[0013] Furthermore, the base is any one or more of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium pivalate, potassium pivalate, cesium pivalate, tripotassium phosphate, potassium formate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide, and cesium pivalate is preferred in the present invention.

[0014] Furthermore, the additive is any one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, adamantanecarboxylic acid, pivalic acid, acetic acid, and benzoic acid. In the present invention, tetrabutylammonium bromide and adamantanecarboxylic acid are preferred.

[0015] Furthermore, the solvent is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 2-methyltetrahydrofuran, ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,3-dioxane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkanes, C 3-12 Fluorinated or chlorinated alkanes, benzene, toluene, xylene, trimethylbenzene, trifluorotoluene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methylpyrrolidone, ethyl acetate, acetonitrile, C 3-12 Any one or more of the saturated alkyl nitriles, preferably dimethyl sulfoxide and tetrahydrofuran.

[0016] Furthermore, when synthesizing an octa-membered aryl silicon heterocycle according to the present invention, the preferred molar ratio of the feed materials is 1.0:1.5:0.05:0.1:2.0:0.25 for the aryl halide A:silacyclobutane B:catalyst C:phosphine ligand D:base E:additive F; and when synthesizing an octa-membered alkenyl silicon heterocycle, the preferred molar ratio of the feed materials is 1.0:1.5:0.05:0.1:1.5:0.5 for the aryl halide A:silacyclobutane B:catalyst C:phosphine ligand D:base E:additive F.

[0017] Furthermore, the reaction temperature is 30-100°C, and the reaction time is 1-40 hours. The heating process can be carried out using an oil bath (such as silicone oil, paraffin oil, etc.) or other heating methods. In the present invention, the reaction is preferably carried out at 60°C for 16 hours.

[0018] Furthermore, the method for isolating and purifying the product comprises: filtering the reaction mixture, extracting, concentrating, and purifying. The filtration can be performed using a sand core funnel under reduced pressure. The concentration process can be performed using methods such as vacuum distillation, for example, using a rotary evaporator to concentrate under reduced pressure. The purification method can be performed using column chromatography for separation and purification.

[0019] The method of the present invention can efficiently prepare eight-membered aryl silicon heterocycles and alkenyl silicon heterocycles. Compared with the prior art, the present invention has the following advantages:

[0020] i) The method of the present invention can achieve diversified preparation of octa-membered silicon heterocycles using simple and readily available raw materials;

[0021] ii) The method of the present invention has very good regioselectivity;

[0022] iii) The method of the present invention has a wide range of substrate applicability and functional group compatibility;

[0023] iv) The method of the present invention can prepare octa-membered silicon heterocyclic compounds in large quantities (gram level), laying a good foundation for industrial production. DETAILED DESCRIPTION

[0024] The present invention is further described below by way of examples. It should be noted that the present invention is not limited to the following embodiments.

[0025] Example 1: Preparation of Compound I-1

[0026]

[0027] Under argon, palladium trifluoroacetate (1.7 mg, 0.005 mmol), 2-di-tert-butylphosphino-2'-methylbiphenyl (3.1 mg, 0.01 mmol), potassium acetate (19.6 mg, 0.20 mmol), adamantanecarboxylic acid (4.5 mg, 0.025 mmol), and dry dimethyl sulfoxide (2.0 mL) were added to a dry reaction tube equipped with a magnetic stirrer. 1-Bromo-2-(1-phenylvinyl)benzene (25.9 mg, 0.1 mmol) and 1,1-bis(4-methoxyphenyl)silacyclobutane (42.7 mg, 0.15 mmol) were then added. The resulting mixture was reacted at 60°C under argon for 16 hours. After completion of the reaction, the reaction was quenched with water and filtered. The filtrate was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. Compound I-1 was then purified by column chromatography to obtain a white solid, 87% yield. 1H NMR (400MHz, CDCl3): δ7.47(d,J=8.5Hz,3H),7.34-7.30(m,3H),7.22(td,J=7.4,1.3H z,1H),7.17-7.14(m,3H),7.09-7.05(m,3H),6.93(d,J=8.5Hz,2H),6.74(d,J=8.6Hz,2 H),6.00(dd,J=11.6,5.8Hz,1H),3.84(s,3H),3.75(s,3H),2.47-2.37(m,1H),2.34-2. 28(m,1H),2.06-1.97(m,1H),1.95-1.86(m,1H),1.53-1.45(m,1H),1.29-1.22(m,1H); 13 C NMR (100MHz, CDCl3): δ160.47,160.37,146.11,144.13,143.28,137.43,137.05,137.01,136.33,131.05,129.14,128.8 4,127.91,127.67,127.24,126.63,126.20,113.67,113.41,55.14,55.06,29.00,21.45,13.81; HRMS(ESI-TOF):calc'd for C 31 H 31 O2Si + [M+H + ]463.2088,found 463.2082.

[0028] Example 2: Preparation of Compound I-2

[0029]

[0030] The operation steps were the same as those in Example 1, except that the brominated olefin used was 1-bromo-4-fluoro-2-(1-phenylvinyl)benzene (27.7 mg, 0.1 mmol), to obtain compound I-2 (white solid, 78% yield). 1H NMR (400MHz, CDCl3): δ7.48–7.40(m,3H),7.31–7.27(m,2H),7.21–7.13(m,3H),7.06–7.03(m,2H),6.95–6.90(m,3H),6.79–6.72(m,3H),6.00(d d,J=11.4,6.1Hz,1H),3.83(s,3H),3.75(s,3H),2.41–2.29(m,2H),2.0 7–1.99(m,1H),1.95–1.82(m,1H),1.51–1.43(m,1H),1.29–1.21(m,1H); 13 C NMR (100MHz, CDCl3): δ163.74(d,J=247.0Hz),160.56,160.45,148.74(d,J=7 .0Hz),143.15(d,J=2.0Hz),142.51,138.96(d,J=8.0Hz),136.94,136.27,133 .14(d,J=3.0Hz),129.44,128.60,128.02,127.59,126.88,117.75(d,J=19.0H z),113.75,113.59(d,J=19.0Hz),113.45,55.15,55.06,29.01,21.36,13.67; 19 F NMR (376MHz, CDCl3): δ-112.43; HRMS (ESI-TOF): calc'd for C 31 H 30 FO2Si + [M+H + ]481.1994,found 481.1995.

[0031] Example 3: Preparation of Compound I-3

[0032]

[0033] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-3-fluoro-2-(1-phenylvinyl)benzene (27.7 mg, 0.1 mmol), to obtain compound I-3 (white solid, 81% yield). 1H NMR (400MHz, CDCl3): δ7.43 (d, J=8.6Hz, 2H), 7.29–7.23 (m, 4H), 7.14–7.1 1(m,3H),7.09–6.99(m,3H),6.92(d,J=8.5Hz,2H),6.67(d,J=8.5Hz,2H),6 .13(dd,J=11.4,5.9Hz,1H),3.83(s,3H),3.72(s,3H),2.40–2.23(m,2H),2 .12–2.02(m,1H),1.96–1.85(m,1H),1.54–1.46(m,1H),1.28–1.21(m,1H); 13 CNMR (100MHz, CDCl3): δ160.72 (d, J = 247.0Hz) 160.56, 160.43, 141.43, 141.10, 138.43, 136.90, 136.20, 132.80 (d, J = 4.0Hz), 132.61, 132.4 8,130.79,128.59(d,J=8.0Hz),128.49,127.95,126.70,126.03,116. 89(d,J=22.0Hz),113.72,113.34,55.15,55.04,29.22,21.70,13.54; 19 F NMR (376MHz, CDCl3): δ-109.87; HRMS (ESI-TOF): calc'dfor C 31 H 30 FO2Si + [M+H + ]481.1994,found 481.1994.

[0034] Example 4: Preparation of Compound I-4

[0035]

[0036] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-bromo-4-chloro-1-(1-phenylvinyl)benzene (29.4 mg, 0.1 mmol), to obtain compound I-4 (white solid, 84% yield). 1H NMR (400MHz, CDCl3): δ7.44(d,J=8.5Hz,2H),7.40(d,J=2.3Hz,1H),7.31–7.26( m,3H),7.15–7.13(m,3H),7.02–6.96(m,3H),6.93(d,J=8.4Hz,2H),6.73(d,J=8. 5Hz,2H),5.99(dd,J=10.0,7.5Hz,1H),3.84(s,3H),3.74(s,3H),2.37–2.30(m, 2H),2.05–1.98(m,1H),1.92–1.83(m,1H),1.51–1.44(m,1H),1.26–1.23(m,1H); 13 C NMR (100MHz, CDCl3): δ160.47,160.37,146.11,144.13,143.28,137.43,137.05,137.01,136.33,131.05,129.14,128.8 4,127.91,127.67,127.24,126.63,126.20,113.67,113.41,55.14,55.06,29.00,21.45,13.81; HRMS(ESI-TOF):calc'd for C 31 H 30 ClO2Si + [M+H + ]497.1698,found 497.1689.

[0037] Example 5: Preparation of Compound I-5

[0038]

[0039] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-bromo-4-methyl-1-(1-phenylvinyl)benzene (27.3 mg, 0.1 mmol), to obtain compound I-5 (white solid, 88% yield). 1H NMR (400MHz, CDCl3): δ7.47(d,J=8.4Hz,2H),7.33(d,J=8.5Hz,2H),7.29–7.27(m,1H), 7.16–7.12(m,4H),7.09–7.06(m,2H),6.96–6.93(m,3H),6.75(d,J=8.3Hz,2H),5.96(dd ,J=11.6,5.7Hz,1H),3.84(s,3H),3.75(s,3H),2.47–2.38(m,1H),2.33–2.29(m,1H),2 .27(s,3H),2.01–1.92(m,1H),1.91–1.84(m,1H),1.51–1.43(m,1H),1.25–1.19(m,1H); 13 C NMR (100MHz, CDCl3): δ160.41,160.34,144.04,143.61,143.21,137.50,137.03,136.35,135.50,131.05,130.09,128.8 5,128.65,127.90,127.70,127.52,126.56,113.64,113.40,55.14,55.06,29.00,21.43,13.95; HRMS(ESI-TOF):calc'd for C 32 H 33 O2Si + [M+H + ]477.2244,found 477.2248.

[0040] Example 6: Preparation of Compound I-6

[0041]

[0042] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-bromo-4-methoxy-1-(1-phenylvinyl)benzene (28.9 mg, 0.1 mmol), to obtain compound I-6 (white solid, 83% yield). 1H NMR (400MHz, CDCl3): δ7.47(d,J=8.5Hz,2H),7.32(d,J=8.5Hz,2H),7.17–7.13(m,3H),7.08–7. 06(m,2H),7.01–6.97(m,2H),6.92(d,J=8.3Hz,2H),6.85(dd,J=8.5,2.9Hz,1H),6.74(d,J=8.3 Hz,2H),5.95(dd,J=11.5,5.8Hz,1H),3.82(s,3H),3.73(s,3H),3.68(s,3H),2.45–2.35(m,1H) ,2.32–2.27(m,1H),2.09–1.93(m,1H),1.91–1.85(m,1H),1.51–1.43(m,1H),1.29–1.20(m,1H); 13 CNMR (100MHz, CDCl3): δ160.48,160.38,157.62,143.70,143.62,139.07,138.43,137.00,136.34,132.33,128.60,128.58,1 27.88,127.69,127.13,126.58,122.24,114.48,113.69,113.41,55.14,55.06,29.09,21.51,13.74; HRMS(ESI-TOF):calc'd for C 32 H 33 O3Si + [M+H + ]493.2193,found 493.2192.

[0043] Example 7: Preparation of Compound I-7

[0044]

[0045] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-4,5-difluoro-2-(1-phenylvinyl)benzene (29.5 mg, 0.1 mmol), to obtain compound I-7 (white solid, 92% yield). 1H NMR (400MHz, CDCl3): δ7.42(d,J=8.6Hz,2H),7.27(d,J=8.4Hz,2H),7.24–7.20(m, 1H),7.18–7.13(m,3H),7.01–6.99(m,2H),6.93(d,J=8.6Hz,2H),6.88–6.83(m,1H ),6.72(d,J=8.6Hz,2H),6.02–5.96(m,1H),3.83(s,3H),3.73(s,3H),2.35–2.29( m,2H),2.08–1.99(m,1H),1.95–1.85(m,1H),1.51–1.43(m,1H),1.25–1.21(m,1H); 13 C NMR (100MHz, CDCl3): δ160.76, 160.59, 150.93 (dd, J = 250.0, 13.0Hz), 149.13 (dd, J =249.0,12.0Hz),143.23(dd,J=6.0,5.0Hz),142.47,142.23,136.90,136.24,135.2 5(dd,J=4.0,2.0Hz),129.71,128.07,127.77,127.50,127.02,126.06,125.00(d,J= 15.0Hz), 119.89 (d, J = 15.4Hz), 113.95, 113.54, 55.17, 55.07, 29.05, 21.32, 13.45;

[0046] 19 F NMR (376MHz, CDCl3): δ-136.93 (d, J=18.8Hz), -140.86 (d, J=22.6Hz); HRMS (ESI-TOF): calc'd for C 31 H 28 F2NaO2Si + [M+H + ]493.2193,found 493.2192.

[0047] Example 8: Preparation of Compound I-8

[0048]

[0049] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-4,5-dimethoxy-2-(1-phenylvinyl)benzene (31.9 mg, 0.1 mmol), to obtain compound I-8 (white solid, 85% yield). 1H NMR (400MHz, CDCl3): δ7.50–7.47(m,2H),7.35–7.31(m,2H),7.18–7.10(m,5H),6.9 5–6.91(m,3H),6.76–6.72(m,2H),6.57–6.55(m,1H),5.96(dd,J=11.4,5.7Hz,1H), 3.83(s,3H),3.74(s,3H),3.72(s,3H),3.66(s,3H),2.47–2.39(m,1H),2.32–2.23( m,1H),1.99–1.95(m,1H),1.89–1.82(m,1H),1.47–1.41(m,1H),1.28–1.18(m,1H); 13 C NMR (100MHz, CDCl3): δ160.41,160.32,149.68,147.19,143.71,143.09,139.47,136.96,136.26,129.06,128.69,128.54,127.89, 127.59,127.45,126.64,119.02,114.00,113.59,113.36,55.77,55.72,55.12,55.03,29.06,21.52,13.65; HRMS(ESI-TOF):calc'd for C 33 H 35 O4Si + [M+Na + ]521.1719,found 521.1728.

[0050] Example 9: Preparation of Compound I-9

[0051]

[0052] The operation steps are the same as those in Example 1, except that the brominated olefin used is 5-bromo-6-(1-phenylvinyl)benzo[d][1,3]dioxole (30.3 mg, 0.1 mmol), to obtain compound I-9 (white solid, 84% yield). 1H NMR (400MHz, CDCl3): δ7.47–7.41(m,2H),7.33–7.30(m,2H),7.16–7.14(m,3H),7.08–7.0 5(m,2H),6.92(dd,J=8.4,1.7Hz,2H),6.88(d,J=1.9Hz,1H),6.73(dd,J=8.6,1.7Hz,2H),6 .53(d,J=1.9Hz,1H),5.97–5.92(m,3H),3.83(s,3H),3.74(s,3H),2.50–2.39(m,1H),2.34 –2.27(m,1H),2.06–1.99(m,1H),1.93–1.82(m,1H),1.51–1.37(m,1H),1.25–1.18(m,1H); 13 C NMR (100MHz, CDCl3): δ160.49,160.36,148.70,146.35,143.55,143.01,140.72,136.93,136.26,130.28,128.94,128.90,127.9 1,127.63,127.25,126.67,115.58,113.75,113.37,111.51,100.98,55.16,55.06,29.02,21.46,13.69; HRMS(ESI-TOF):calc'd forC 32 H 31 O4Si + [M+H + ]507.1986,found507.1984.

[0053] Example 10: Preparation of Compound I-10

[0054]

[0055] The operation steps were the same as those in Example 1, except that the brominated olefin used was 3-bromo-4-(1-phenylvinyl)pyridine (26 mg, 0.1 mmol), to obtain compound I-10 (oily liquid, 35% yield). 1H NMR (400MHz, CDCl3): δ8.61(s,1H),8.51(d,J=5.2Hz,1H),7.45(d,J=8.5Hz,2H),7. 31(d,J=8.5Hz,2H),7.19–7.17(m,3H),7.02–6.90(m,2H),6.97–6.92(m,3H),6.75( d,J=8.5Hz,2H),6.06(dd,J=11.1,6.5Hz,1H),3.83(s,3H),3.74(s,3H),2.37–2.27 (m,2H),2.07–1.98(m,1H),1.94–1.85(m,1H),1.54–1.46(m,1H),1.35–1.26(m,1H); 13 C NMR (100MHz, CDCl3): δ160.82,160.66,157.08,154.37,149.84,142.27,141.71,136.99,136.31,132.63,130.34,128.1 9,127.59,127.20,126.95,126.08,125.69,113.98,113.66,55.20,55.10,29.02,21.12,13.49; HRMS(ESI-TOF):calc'd for C 30 H 30 NO2Si + [M+H + ]464.2040,found 464.2048.

[0056] Example 11: Preparation of Compound I-11

[0057]

[0058] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-2-[1-(4-methylphenyl)vinyl]benzene (27.3 mg, 0.1 mmol), to obtain compound I-11 (white solid, 86% yield). 1H NMR (400MHz, CDCl3): δ7.46–7.44(m,3H),7.32–7.28(m,3H),7.19(td,J=7.4,1.3Hz,1 H),7.05-7.03(m,1H),6.98–6.95(m,4H),6.91(d,J=8.5Hz,2H),6.73(d,J=8.5Hz,2H) ,5.94(dd,J=11.6,5.8Hz,1H),3.82(s,3H),3.74(s,3H),2.45-2.36(m,1H),2.35-2.2 5(m,4H),2.01-1.94(m,1H),1.91-1.82(m,1H),1.50-1.41(m,1H),1.26-1.19(m,1H); 13 C NMR (100MHz, CDCl3): δ160.46,160.37,146.33,144.01,140.65,137.35,137.02,136.36,136.32,131.06,129.12,128.93,1 28.65,128.08,127.61,127.38,126.12,113.66,113.41,55.15,55.06,28.93,21.45,21.16,13.87; HRMS(ESI-TOF):calc'd for C 32 H 33 O2Si + [M+H + ]477.2244,found447.2245.

[0059] Example 12: Preparation of Compound I-12

[0060]

[0061] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-2-[1-(4-fluorophenyl)vinyl]benzene (27.7 mg, 0.1 mmol), to obtain compound I-12 (white solid, 75% yield). 1H NMR (400MHz, CDCl3): δ7.50–7.42(m,3H),7.33(td,J=7.5,1.5Hz,1H),7.30–7.27(m,2H),7.22( td,J=7.4,1.3Hz,1H),7.03(dd,J=7.8,1.2Hz,1H),7.01–6.96(m,2H),6.93(d,J=8.5Hz,2H),6.8 2(t,J=8.7Hz,2H),6.72(d,J=8.5Hz,2H),5.93(dd,J=10.9,6.5Hz,1H),3.83(s,3H),3.74(s,3H) ,2.39–2.24(m,2H),2.06–2.01(m,1H),1.95–1.84(m,1H),1.51–1.44(m,1H),1.34–1.21(m,1H); 13 C NMR (100MHz, CDCl3): δ161.94(d,J=244.0Hz),160.50,160.41,145.85,143.01,139.09(d,J=3.1Hz),137.60,137.12,136.98,136.27,1 30.81,129.22,128.99(d,J=8.0Hz),128.72,127.02,126.37,114.62(d,J=22.0Hz),113.70,113.37,55.15,55.06,29.03,21.58,13.70; 19 F NMR (376MHz, CDCl3): δ-116.66; HRMS (ESI-TOF): calc'd forC 31 H 30 FO2Si + [M+H + ]481.1994,found 481.2001.

[0062] Example 13: Preparation of Compound I-13

[0063]

[0064] The operation steps are the same as those in Example 1, except that the brominated olefin used is 1-bromo-2-[1-(4-trifluoromethylphenyl)vinyl]benzene (32.7 mg, 0.1 mmol), to obtain compound I-13 (white solid, 21% yield). 1H NMR (400MHz, CDCl3): δ7.49–7.42(m,3H),7.41–7.32(m,3H),7.29–7.23(m,3H),7 .11(d,J=8.1Hz,2H),7.01(dd,J=7.8,1.3Hz,1H),6.92(d,J=8.6Hz,2H),6.68(d,J =8.6Hz,2H),6.08(dd,J=10.0,7.3Hz,1H),3.83(s,3H),3.71(s,3H),2.40–2.29(m ,2H),2.12–2.03(m,1H),2.00–1.86(m,1H),1.52–1.42(m,1H),1.28–1.25(m,1H); 13 C NMR (100MHz, CDCl3): δ160.55,160.44,145.10,142.91,137.88,137.23,136.96,136.25,131.06,130.73,129.3 4,128.44,127.53,126.75,126.61,124.79(q,J=274.0Hz),113.73,113.39,55.16,54.99,29.15,21.54,13.62; 19 F NMR (376MHz, CDCl3): δ-62.31; HRMS (ESI-TOF): calc'd forC 32 H 29 F3NaO2Si + [M+Na + ]553.1781,found 553.1786.

[0065] Example 14: Preparation of Compound I-14

[0066]

[0067] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-[1-(2-bromophenyl)vinyl]naphthalene (30.9 mg, 0.1 mmol), to obtain compound I-14 (white solid, 94% yield). 1H NMR (400MHz, CDCl3): δ7.76–7.71(m,1H),7.63–7.54(m,2H),7.50–7.47(m,3H),7.40–7.36(m ,2H),7.36–7.32(m,2H),7.31–7.29(m,2H),7.26–7.24(m,2H),7.10(d,J=7.6Hz,1H),6.92(d, J=8.2Hz,2H),6.61(d,J=8.3Hz,2H),6.11(dd,J=11.2,6.2Hz,1H),3.82(s,3H),3.56(s,3H),2 .47–2.31(m,2H),2.07–2.03(m,1H),1.98–1.97(m,1H),1.54–1.45(m,1H),1.32–1.23(m,1H); 13 C NMR (100MHz, CDCl3): δ160.49,160.28,146.03,144.04,140.32,137.78, 137.01,136.35,133.30,132.46,131.01,129.68,129.24,128.77,128.2 5,127.47,127.29,127.00,126.76,126.34,125.92,125.67,125.59,113.70,113.28,55.16,54.90,29.09,21.68,13.72; HRMS(ESI-TOF):calc'd for C 35 H 33 O2Si + [M+H + ]513.2244,found 513.2240.

[0068] Example 15: Preparation of Compound I-15

[0069]

[0070] The operation steps are the same as those in Example 1, except that the brominated olefin used is 5-[1-(2-bromophenyl)vinyl]-2-ethoxypyridine (30.4 mg, 0.1 mmol), to obtain compound I-15 (white solid, 74% yield). 1H NMR (400MHz, CDCl3): δ7.84(d,J=2.5Hz,1H),7.46–7.42(m,3H),7.32(td,J=7.5,1.5Hz,1H),7.28–7.18( m,3H),7.16–7.13(m,1H),7.05(dd,J=7.8,1.2Hz,1H),6.91(d,J=8.5Hz,2H),6.68(d,J=8.5Hz,2H),6.45 (d,J=8.7Hz,1H),5.89(dd,J=9.7,7.6Hz,1H),4.33–4.27(m,2H),3.81(s,3H),3.71(s,3H),2.34–2.20(m ,2H),2.08–2.04(m,1H),1.93–1.84(m,1H),1.53–1.43(m,1H),1.37(t,J=7.0Hz,3H),1.31–1.22(m,1H); 13 C NMR (100MHz, CDCl3): δ162.73,160.48,160.33,145.44,145.19,140.65,137.65,137.33,137.20,136.93,136.19,131.54,130.56,129. 31,128.69,128.13,126.76,126.49,113.69,113.32,109.95,61.73,55.14,55.00,29.01,21.77,14.84,13.55; HRMS(ESI-TOF):calc'd for C 32 H 34 NO3Si + [M+H + ]508.2302,found 508.2306.

[0071] Example 16: Preparation of Compound I-16

[0072]

[0073] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-[1-(2-bromophenyl)vinyl]-2-thiophene (26.5 mg, 0.1 mmol), to obtain compound I-16 (white solid, 32% yield). 1H NMR (400MHz, CDCl3): δ7.43(d,J=8.6Hz,2H),7.37(d,J=7.4Hz,2H),7.27–7.25(m,1H),7.24–7 .22(m,1H),7.17(d,J=8.5Hz,2H),7.04(dd,J=5.1,3.0Hz,1H),6.90(d,J=8.6Hz,2H),6.81(dd, J=5.1,1.3Hz,1H),6.66–6.55(m,3H),5.90(dd,J=11.3,5.9Hz,1H),3.81(s,3H),3.71(s,3H), 2.30–2.22(m,1H),2.16–2.00(m,2H),1.90–1.75(m,1H),1.54–1.44(m,1H),1.30–1.22(m,1H); 13 C NMR (100MHz, CDCl3): δ160.42,160.19,145.52,144.15,138.94,137.43,137.17,136.88,135.75,130.12,129.10,128.89,1 28.04,126.52,126.19,125.74,124.54,121.82,113.66,112.87,55.14,55.03,28.84,22.13,13.17; HRMS(ESI-TOF):calc'd forC 29 H 29 O2SSi + [M+H + ]469.1652,found469.1646.

[0074] Example 17: Preparation of Compound I-17

[0075]

[0076] The operation steps were the same as those in Example 1, except that the brominated olefin used was methyl 2-(2-bromophenyl)acrylate (24.1 mg, 0.1 mmol), to obtain compound I-17 (white solid, 58% yield). 1H NMR (400MHz, CDCl3): δ7.42–7.38(m,3H),7.31–7.21(m,4H),6.89(d,J=8.6Hz,2H),6.84–6.78(m,3H),3.80(s,3H),3. 78(s,3H),3.53(s,3H),2.33–2.17(m,2H),2.02–1.92(m,1H),1.85–1.74(m,1H),1.56–1.50(m,1H),1.35–1.27(m,1H); 13 C NMR (100MHz, CDCl3): δ167.20,160.51,160.42,143.79,140.81,137.46,136.88,136.79,135.98,135.90,130.49,1 28.97,128.27,126.92,126.57,113.71,113.57,55.11,55.06,51.76,29.09,20.95,12.76; HRMS(ESI-TOF):calc'd forC 27 H 28 NaO4Si + [M+Na + ]467.1649,found 467.1652.

[0077] Example 18: Preparation of Compound I-18

[0078]

[0079] The operation steps are the same as those in Example 1, except that the brominated olefin used is 2-(2-bromophenyl)acrylonitrile (20.8 mg, 0.1 mmol), to obtain compound I-18 (white solid, 40% yield). 1 H NMR (400MHz, CDCl3): δ7.50–7.44(m,2H),7.40–7.36(m,3H),7.32–7.27(m,3H),6.93–6.90(m,4H),6.46(dd,J=11.3,6.9Hz,1H),3.82( s,3H),3.80(s,3H),2.31–2.25(m,1H),2.23–2.16(m,1H),2.09–2.03(m,1H),1.79–1.70(m,1H),1.53–1.47(m,1H),1.35–1.29(m,1H); 13C NMR (100MHz, CDCl3): δ160.77,148.12,138.05,137.96,136.92,136.84,136.17,130.01,129.22,128.2 2,127.27,125.71,119.92,118.53,114.14,113.89,55.16,29.05,20.11,12.90; HRMS(ESI-TOF):calc'd for C 26 H 26 NO2Si + [M+H + ]412.1727,found 412.1725.

[0080] Example 19: Preparation of Compound I-19

[0081]

[0082] The operation steps are the same as those in Example 1, except that the brominated olefin used is (E)-1-(2-bromophenyl)-2-phenylethylene (33.5 mg, 0.1 mmol), to obtain compound I-19 (white solid, 74% yield). 1 H NMR (400MHz, CDCl3): δ7.52–7.47(m,5H),7.27–7.23(m,1H),7.18–7.08(m,4H),7.01(dd,J=7.5,1.9Hz,2H),6.98–6.90(m,8H),6.70–6.67(m,2H ),3.86(s,3H),3.84(s,3H),3.09(td,J=12.7,5.3Hz,1H),2.79–2.74(m, 1H),1.92–1.85(m,1H),1.73–1.55(m,2H),1.28(dt,J=14.6,4.3Hz,1H); 13 C NMR (100MHz, CDCl3): δ160.76,160.51,149.81,143.82,141.68,141.65,138.67,137.12,136.99,136.91,136.71,131.70,131.37,129.94,1 29.39,129.23,127.85,127.71,127.40,126.36,125.78,125.76,113.85,113.71,55.20,55.15,33.99,19.61,13.14; HRMS(ESI-TOF):calc'd for C 37 H 34KO2Si + [M+K + ]577.1960,found 577.1955.

[0083] Example 20: Preparation of Compound I-20

[0084]

[0085] The operation steps were the same as those in Example 1, except that the silacyclobutane used was 1,1-bis(4-N,N-dimethylphenyl)silacyclobutane (46.6 mg, 0.15 mmol), to obtain compound I-20 (white solid, 72% yield). 1 H NMR (400MHz, CDCl3): δ7.54(dd,J=7.5,1.5Hz,1H),7.43(d,J=8.6Hz,2H),7.27(d,J=8.8Hz,2H ),7.24–7.22(m,1H),7.20–7.12(m,4H),7.11–7.08(m,2H),7.00(dd,J=7.7,1.4Hz,1H),6.73(d ,J=8.7Hz,2H),6.58(d,J=8.7Hz,2H),5.96(dd,J=11.8,5.6Hz,1H),2.96(s,6H),2.89(s,6H), 2.55–2.44(m,1H),2.30–2.23(m,1H),2.00–1.81(m,2H),1.48–1.40(m,1H),1.22–1.16(m,1H); 13 C NMR (100MHz, CDCl3): δ150.92,150.88,146.04,144.38,144.06,138.44,137.17,136.79,136.07,130.99,128.91,128.7 0,127.99,127.91,126.46,125.96,123.37,122.30,111.89,40.34,40.31,28.94,21.47,14.13; HRMS(ESI-TOF):calc'd for C 33 H 37 N2Si + [M+H + ]489.2721,found 489.2722.

[0086] Example 21: Preparation of Compound I-21

[0087]

[0088] The operation steps were the same as those in Example 1, except that the silacyclobutane used was 1,1-bis(2-naphthyl)silacyclobutane (48.7 mg, 0.15 mmol), to obtain compound I-21 (white solid, 88% yield). 1 H NMR (400MHz, CDCl3): δ8.04(s,1H),7.93(s,1H),7.86–7.83(m,2H),7.76(t,J=7.2Hz,2H), 7.70–7.62(m,3H),7.56–7.47(m,4H),7.45–7.35(m,3H),7.22(td,J=7.5,1.3Hz,1H),7.12 (d,J=7.7Hz,1H),7.07–7.00(m,5H),6.03(dd,J=11.5,5.9Hz,1H),2.50–2.43(m,1H),2.41 –2.34(m,1H),2.14–2.08(m,1H),2.02–1.95(m,1H),1.76–1.69(m,1H),1.51–1.44(m,1H); 13 C NMR (100MHz, CDCl3):146.27,144.15,142.88,137.32,136.67,136.56,135.95,135 .21,133.84,133.82,133.46,133.07,132.90,131.71,131.17,131.04,129.45,128 .89,128.40,128.32,127.87,127.83,127.69,127.51,127.16,126.95,126.76,126 .66,126.45,126.40,126.04,125.73,29.21,21.58,13.59; HRMS(ESI-TOF):calc'd for C 25 H 23 S2Si + [M+H + ]503.2190,found503.2187.

[0089] Example 22: Preparation of Compound I-22

[0090]

[0091] The operation steps were the same as those in Example 1, except that the silacyclobutane used was 1,1-bis(3-thienyl)silacyclobutane (35.5 mg, 0.15 mmol), to obtain compound I-22 (white solid, 37% yield). 1H NMR (400MHz, CDCl3): δ7.48–7.45(m,2H),7.34–7.30(m,2H),7.27–7.20(m,4H),7.17–7.14(m,3H),7.09–7.07(m,1H),7.05–7.02(m ,3H),6.00(dd,J=10.9,6.6Hz,1H),2.42–2.30(m,2H),2.09–2.00(m,1H),1.96–1.85(m,1H),1.52–1.44(m,1H),1.31–1.24(m,1H); 13 C NMR (100MHz, CDCl3):145.80,144.23,143.20,138.25,137.13,136.89,136.37,134.17,133.64,132.76,132.30,130 .94,129.47,129.03,127.95,127.62,126.78,126.45,125.98,125.47,29.06,21.57,14.40; HRMS(ESI-TOF):calc'd for C 25 H 23 S2Si + [M+H + ]415.1005,found 415.1008.

[0092] Example 23: Preparation of Compound I-23

[0093]

[0094] The operation steps were the same as those in Example 1, except that the silacyclobutane used was 1,1-bis(n-butyl)silacyclobutane (27.7 mg, 0.15 mmol), to obtain compound I-23 (white solid, 83% yield). 1 H NMR (400MHz, CDCl3): δ7.58–7.54(m,1H),7.31–7.19(m,7H),7.01–6.98(m,1H),6.09(dd,J=11.3,6.0Hz,1H),2.26–2.19(m,1H),2. 02–1.90(m,2H),1.68–1.59(m,1H),1.46–1.36(m,4H),1.14–1.04(m,4H),0.97–0.89(m,6H),0.70–0.64(m,4H),0.62–0.58(m,2H); 13C NMR (100MHz, CDCl3): δ145.60,143.94,143.50,139.62,134.39,130.53,129.42,128.60,128.09,127.75,126.8 6,126.37,29.44,27.19,26.59,26.50,26.31,22.12,14.01,13.76,13.43,13.29,12.57; HRMS(ESI-TOF):calc'd for C 25 H 35 Si + [M+H + ]363.2503,found 363.2500.

[0095] Example 24: Preparation of Compound I-24

[0096]

[0097] The operation steps were the same as those in Example 1, except that the silacyclobutane used was 1-benzyl-1-methylsilacyclobutane (26.4 mg, 0.15 mmol), to obtain compound I-24 (white solid, 82% yield, 2:1 dr). 1 H NMR(400MHz,CDCl3)(mixture of two diastereoisomers): δ7.71–7.69(m,0.5H),7.58–7.56(m,1H),7.37–7.09(m,15.5H),7.04–7. 00(m,2H),6.85(d,J=7.5Hz,2H),6.12(dd,J=11.4,6.1Hz,1H),6.05(dd,J=11.3,6.2Hz,0.5H) ,2.55(q,J=13.6Hz,1H),2.41–2.35(m,1H),2.30–2.19(m,2H),2.07–2.03(m,1H),2.00–1.91( m,2H),1.72–1.60(m,1IH),0.93–0.83(m,2H),0.63–0.53(m,2H),0.23(s,3H),0.00(s,1.5H); 13C NMR(100MHz,CDCl3)(mixture of twodiastereoisomers): δ145.54,145.24,144.05,143.83,143.41,143.25,140.19,140.17, 139.66,139.11,134.27,133.53,130.32,130.17,129.97,129.55,128.94,128.91,128.73,1 28.34,128.15,128.09,128.05,128.02,127.75,126.88,126.57,126.44,124.12,123.90,29 .54,29.28,25.00,24.58,21.84,21.81,13.28,13.14,-3.37,-4.71; HRMS(ESI-TOF):calc'd for C 25 H 27 Si + [M+H + ]355.1877,found 355.1875.

[0098] Example 25: Preparation of Compound II-1

[0099]

[0100] Under argon protection, palladium trifluoroacetate (1.7 mg, 0.005 mmol), 2-di-tert-butylphosphino-2'-methylbiphenyl (3.1 mg, 0.01 mmol), cesium pivalate (35.0 mg, 0.15 mmol), tetrabutylammonium bromide (16.0 mg, 0.05 mmol), and dry tetrahydrofuran (1.0 mL) were added to a dry reaction tube equipped with a magnetic stirrer. 1-Bromo-2-(3-methylbut-1-en-2-yl)benzene (22.5 mg, 0.1 mmol) and 1,1-bis(4-methoxyphenyl)silacyclobutane (42.7 mg, 0.15 mmol) were then added. The resulting mixture was reacted at 70°C under argon protection for 16 hours. After the reaction, the reaction was quenched with water and then filtered. The filtrate was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The mixture was separated and purified by column chromatography to obtain compound II-1 (colorless oily liquid, 70% yield). 1H NMR (400MHz, CDCl3): δ7.55 (d, J = 8.0Hz, 2H), 7.23-7.09 (m, 5H), 7.17-7.13 ( m,1H),6.97(d,J=8.0Hz,2H),6.77(d,J=8.0Hz,2H),6.18(s,1H),3.85(s,3H) ,3.76(s,3H),3.09-3.01(m,1H),2.76-2.67(m,2H),1.97-1.88(m,2H),1.26( d,J=6.7Hz,3H),0.99-0.88(m,1H),0.89(d,J=6.9Hz,3H),0.57-0.48(m,1H); 13 C NMR (100MHz, CDCl3): δ164.15,160.50,160.23,143.73,139.19,136.29,136.01,128.71,128.58,128.52,127.63,127 .14,125.39,120.69,113.82,113.40,55.15,55.07,39.37,31.29,24.99,22.11,21.50,11.22; HRMS(ESI-TOF):calc'd for C 28 H 33 O2Si + [M+H + ]429.2244,found 429.2241.

[0101] Example 26: Preparation of Compound II-2

[0102]

[0103] The operation steps were the same as those in Example 25, except that the brominated olefin used was 1-bromo-2-(1-cyclopropylvinyl)benzene (22.3 mg, 0.1 mmol), to obtain compound II-2 (colorless oily liquid, 63% yield). 1H NMR (400MHz, CDCl3): δ7.52(d,J=8.0Hz,2H),7.36(d,J=7.5Hz,1H),7.22–7.07(m,5 H),5.96(d,J=8.0Hz,2H),6.76(d,J=8.0Hz,2H),5.97(s,1H),3.84(s,3H),3.75(s, 3H),3.05(td,J=12.4,6.1Hz,1H),2.71–2.65(m,1H),1.98–1.83(m,2H),1.71–1.69 (m,1H),0.98-0.94(m,1H),0.90–0.83(m,1H),0.75–0.62(m,2H),0.61–0.46(m,2H); 13 C NMR (100MHz, CDCl3): δ160.53,160.27,159.19,142.70,138.77,136.32,136.00,128.95,128.58,128.46,128.26,12 7.40,125.28,119.70,113.82,113.44,55.16,55.08,31.28,24.99,22.35,11.09,9.01,7.36; HRMS(ESI-TOF):calc'd for C 28 H 31 O2Si + [M+H + ]427.2088, found 427.2095.

[0104] Example 27: Preparation of Compound II-3

[0105]

[0106] The operation steps are the same as those in Example 25, except that the brominated olefin used is 1-bromo-2-(1-cyclohexylvinyl)benzene (26.5 mg, 0.1 mmol), to obtain compound II-3 (colorless oily liquid, 68% yield). 1H NMR (400MHz, CDCl3): δ7.54(d,J=8.5Hz,2H),7.21–7.09(m,6H),6.96(d,J=8.6Hz,2H ),6.76(d,J=8.8Hz,2H),6.14(s,1H),3.84(s,3H),3.75(s,3H),3.05(td,J=12.5,5.8 Hz,1H),2.69–2.64(m,1H),2.30(t,J=11.4Hz,1H),2.02–1.85(m,4H),1.66–1.53(m, 3H),1.51–1.31(m,2H),1.23–1.10(m,2H),0.96(d,J=14.7Hz,2H),0.54–0.46(m,1H); 13 C NMR (100MHz, CDCl3): δ163.45,160.49,160.22,143.92,139.25,136.30,136.02,128.65,128.61,128.59,127.64,127.09,125.4 2,121.34,113.81,113.40,55.16,55.06,49.64,32.91,32.12,31.31,27.15,26.69,26.55,25.00,11.28; HRMS(ESI-TOF):calc'd for C 31 H 37 O2Si + [M+H + ]469.2557,found469.2561.

[0107] Example 28: Preparation of Compound II-4

[0108]

[0109] The operation steps are the same as those in Example 25, except that the brominated olefin used is 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol), to obtain compound II-4 (white solid, 73% yield). 1H NMR (400MHz, CDCl3): δ7.49 (d, J = 8.4Hz, 2H), 7.17-7.07 (m, 4H), 7.07-7.05 (m,1H),6.99-6.90(m,3H),6.72(d,J=8.4Hz,2H),6.38(s,1H),3.82(s,3H), 3.75(s,3H),2.95(td,J=12.4,5.6Hz,1H),2.73-2.68(m,1H),2.05-2.01(m ,1H),1.90-1.81(m,1H),1.12(s,9H),0.98-0.87(m,1H),0.48-0.39(m,1H); 13 CNMR (100MHz, CDCl3): δ167.22,160.40,160.11,141.57,139.74,136.16,136.01,129.34,128.84,128.80,128.16, 127.11,124.26,122.97,113.76,113.21,55.13,55.04,39.14,31.55,30.27,25.51,11.63; HRMS(ESI-TOF):calc'd for C 29 H 35 O2Si + [M+H + ]443.2401,found 443.2406.

[0110] Example 29: Preparation of Compound II-5

[0111]

[0112] The operation steps are the same as those in Example 25, except that the brominated olefin used is 2-bromo-1-(3,3-dimethylbut-1-en-2-yl)-4-fluorobenzene (25.7 mg, 0.1 mmol), to obtain compound II-5 (colorless oily liquid, 87% yield). 1H NMR (400MHz, CDCl3): δ7.48(d,J=8.5Hz,2H),7.12(d,J=8.5Hz,2H),6.97-6.92(m,3H) ,6.87(dd,J=10.0,2.7Hz,1H),6.75(d,J=8.6Hz,2H),6.63(td,J=8.5,2.7Hz,1H),6.41 (s,1H),3.83(s,3H),3.77(s,3H),2.94(td,J=12.3,5.2Hz,1H),2.71-2.65(m,1H),2. 16-2.03(m,1H),1.96-1.78(m,1H),1.13(s,9H),0.97-0.91(m,1H),0.57-0.49(m,1H); 13 C NMR (100MHz, CDCl3): δ166.42, 161.92 (d, J = 243.0Hz), 160.44, 160.19, 142.42 (d, J = 7.0Hz), 137.47 (d, J = 4.0Hz), 136.10, 135.90, 130.34 (d, J = 7.0Hz),129.18,127.80,123.83,114.97(d,J=20.0Hz),113.78,113.24, 111.42(d,J=21.0Hz),55.12,55.06,39.09,31.91,30.14,25.57,11.66; 19 F NMR (376MHz, CDCl3): δ-116.55; HRMS (ESI-TOF): calc'dfor C 29 H 34 FO2Si + [M+H + ]461.2307,found 461.2310.

[0113] Example 30: Preparation of Compound II-6

[0114]

[0115] The operation steps are the same as those in Example 25, except that the brominated olefin used is 5-bromo-6-(3,3-dimethylbut-1-en-2-yl)benzo[d][1,3]dioxole (28.3 mg, 0.1 mmol) to obtain compound II-6 (colorless oily liquid, 51% yield). 1H NMR (400MHz, CDCl3): δ7.43(d,J=8.5Hz,2H), 7.09(d,J=8.5Hz,2H), 6.89(d,J=8.5Hz,2H), 6.72(d,J=8.5Hz,2H),6.55(s,1H),6.33(s,1H),6.29(s,1H),5.85(d,J=1.5Hz,1H),5.68( d,J=1.6Hz,1H),3.79(s,3H),3.76(s,3H),2.77(td,J=12.6,3.9Hz,1H),2.59-2.53(m,1H) ,2.19-2.10(m,1H),1.90-1.72(m,1H),1.12(s,9H),0.97-0.82(m,1H),0.80-0.73(m,1H); 13 C NMR (100MHz, CDCl3): δ167.33,160.35,159.94,146.51,144.02,136.00,135.98,134.99,133.54,130.01,127.44,123. 60,113.70,112.92,108.86,108.66,100.68,55.15,55.07,38.90,32.00,30.31,26.43,11.87; HRMS(ESI-TOF):calc'd forC 30 H 35 O4Si + [M+Na + ]487.2299,found487.2300.

[0116] Example 31: Preparation of Compound II-7

[0117]

[0118] The operation steps are the same as those in Example 25, except that the brominated olefin used is 1-bromo-2-(cyclopent-1-en-1-yl)benzene (22.3 mg, 0.1 mmol), to obtain compound II-7 (white solid, 52% yield). 1H NMR (400MHz, CDCl3): δ7.39 (d, J=8.6Hz, 2H), 7.33 (td, J=7.4, 1.5Hz, 1H), 7.28-7.22 (m, 3H), 7.20(dd,J=8.1,1.5Hz,1H),7.13(td,J=7.4,1.3Hz,1H),6.89(d,J=8.5Hz,2H),6.84(d,J=8.5 Hz,2H),3.80(s,3H),3.79(s,3H),2.79-2.63(m,1H),2.23-2.17(m,2H),2.13-1.92(m,4H),1 .79-1.72(m,1H),1.68-1.60(m,1H),1.52-1.45(m,1H),1.36-1.26(m,1H),0.97-0.86(m,1H); 13 CNMR (100MHz, CDCl3): δ160.35,160.32,145.56,140.06,138.75,137.36,136.83,135.98,135.75,129.36,129.10,127 .42,127.19,125.94,113.62,113.42,55.17,55.13,38.72,36.69,29.31,21.89,19.77,13.61; HRMS(ESI-TOF):calc'd for C 28 H 31 O2Si + [M+H + ]427.2088,found 427.2096.

[0119] Example 32: Preparation of Compound II-8

[0120]

[0121] The operation steps were the same as those in Example 25, except that the brominated olefin used was 2'-bromo-2,3,4,5-tetrahydro-1,1'-biphenyl (23.7 mg, 0.1 mmol), to obtain compound II-8 (colorless oily liquid, 53% yield). 1H NMR (400MHz, CDCl3): δ7.43(d,J=8.5Hz,2H),7.30(d,J=8.6Hz,2H),7.17-7.08(m,3H ),7.06-7.02(m,1H),6.91(d,J=8.6Hz,2H),6.82(d,J=8.6Hz,2H),3.82(s,3H),3.79( s,3H),3.17(td,J=12.5,5.7Hz,1H),2.78-2.73(m,1H),2.60-2.50(m,1H),2.17-1.9 7(m,4H),1.92-1.74(m,2H),1.73-1.51(m,3H),0.91-0.84(m,1H),0.43-0.35(m,1H); 13 C NMR (100MHz, CDCl3): δ160.25,160.22,149.32,145.02,138.03,136.84,136.30,132.92,128.72,128.44,127.29,126 .86,125.48,113.52,113.43,55.11,55.09,35.64,31.44,30.91,26.99,25.20,23.52,12.92; HRMS(ESI-TOF):calc'd for C 29 H 33 O2Si + [M+H + ]441.2244,found 441.2240.

[0122] Example 33: Preparation of Compound II-9

[0123]

[0124] The operation steps are the same as those in Example 25, except that the brominated olefin used is 4-(2-bromophenyl)-1-methyl-1,2,3,6-tetrahydropyridine (25.2 mg, 0.1 mmol), to obtain compound II-9 (colorless oily liquid, 69% yield). 1H NMR (400MHz, CDCl3): δ7.42(d,J=8.5Hz,2H),7.30(d,J=8.5Hz,2H),7.16-7.07(m,3H),7 .05-7.01(m,1H),6.90(d,J=8.5Hz,2H),6.80(d,J=8.6Hz,2H),3.82(s,3H),3.77(s,3H) ,3.15(td,J=12.6,5.5Hz,1H),3.04-2.90(m,3H),2.82-2.73(m,3H),2.68-2.55(m,1H), 2.29(s,3H),2.20-2.05(m,1H),1.90-1.81(m,1H),0.94-0.86(m,1H),0.50-0.42(m,1H); 13 C NMR (100MHz, CDCl3): δ160.47,160.42,146.87,143.30,138.23,136.85,136.29,130.70,128.94,128.23,127.47,127.33 ,126.24,125.67,113.70,113.56,58.76,55.13,55.10,52.34,45.44,35.48,31.48,25.16,12.77; HRMS(ESI-TOF):calc'd for C 29 H 34 NO2Si + [M+H + ]456.2353,found 456.2356.

[0125] Example 34: Preparation of Compound II-10

[0126]

[0127] The operation steps were the same as those in Example 25, except that the brominated olefin used was 4-(2-bromophenyl)-3,6-dihydro-2H-pyran (23.9 mg, 0.1 mmol), to obtain compound II-10 (white solid, 77% yield). 1H NMR (400MHz, CDCl3): δ7.41(d,J=8.4Hz,2H),7.30(d,J=8.4Hz,2H),7.14(d,J=5.0Hz,3H),7.11 –7.06(m,1H),6.91(d,J=8.4Hz,2H),6.82(d,J=8.3Hz,2H),4.20–4.07(m,2H),3.97–3.91(m,1H ),3.90–3.85(m,1H),3.82(s,3H),3.78(s,3H),3.18(td,J=12.6,5.4Hz,1H),2.83–2.77(m,1H) ,2.73–2.65(m,1H),2.25–2.08(m,2H),1.94–1.86(m,1H),0.99–0.93(m,1H),0.56–0.48(m,1H); 13 C NMR (100MHz, CDCl3): δ160.59,160.47,145.82,143.28,138.21,136.81,136.23,132.83,129.04,128.06,127.40,126 .90,126.08,125.76,113.76,113.58,69.66,64.76,55.13,55.09,34.11,31.52,25.19,12.74; HRMS(ESI-TOF):calc'd for C 28 H 31 O3Si + [M+H + ]443.2037,found 443.2044.

[0128] Example 35: Preparation of Compound II-11

[0129]

[0130] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1,1-diphenylsilacyclobutane (33.7 mg, 0.15 mmol). Compound II-11 was obtained as a colorless oily liquid, 84% yield. 1H NMR (400MHz, CDCl3): δ7.60–7.56(m,2H),7.41–7.37(m,3H),7.26–7.21(m,3H),7.2 0–7.16(m,3H),7.12(td,J=7.4,1.4Hz,1H),7.04(d,J=1.4Hz,1H),6.96–6.91(td,J= 7.4,1.4Hz,1H),6.44(s,1H),2.98(td,J=12.4,5.4Hz,1H),2.76–2.71(m,1H),2.16 –2.07(m,1H),1.95–1.86(m,1H),1.17(s,9H),0.99–0.90(m,1H),0.59–0.51(m,1H); 13 C NMR (100MHz, CDCl3): δ167.98,141.47,139.72,138.42,136.78,134.76,134.61,129.02,128.94,128.85,1 28.68,127.99,127.39,127.15,124.29,122.38,39.18,31.63,30.28,25.62,11.30; HRMS(ESI-TOF):calc'd for C 27 H 30 Si + [M+H + ]383.2190,found 383.2192.

[0131] Example 36: Preparation of Compound II-12

[0132]

[0133] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1,1-di(2-naphthyl)silacyclobutane (48.7 mg, 0.15 mmol). Compound II-12 was obtained as a colorless oily liquid, 73% yield. 1H NMR (400MHz, CDCl3): δ8.11(s,1H),7.88–7.82(m,3H),7.78–7.76(m,1H),7.73–7.65(m,4H), 7.52–7.48(m,2H),7.46–7.42(m,2H),7.34(d,J=8.2Hz,1H),7.20(d,J=8.2Hz,1H),7.07–7.03 (m,2H),6.81(td,J=7.5,1.4Hz,1H),6.59(s,1H),3.05(td,J=12.4,5.3Hz,1H),2.81–2.76(m, 1H),2.22–2.18(m,1H),2.08–1.95(m,1H),1.21(s,9H),1.17–1.13(m,1H),0.79–0.71(m,1H); 13 C NMR (100MHz, CDCl3): δ168.39,141.51,139.76,135.88,135.53,135.47,134.2 3,133.82,133.64,133.12,132.80,131.06,130.97,129.03,128.85,128.32,1 28.20,127.84,127.70,127.25,127.23,126.54,126.52,126.22,126.01,125. 65,124.26,122.29,39.25,31.71,30.29,25.83,11.51; HRMS(ESI-TOF):calc'd for C 35 H 35 Si + [M+H + ]483.2503,found 483.2505.

[0134] Example 37: Preparation of Compound II-13

[0135]

[0136] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1,1-bis(3-thienyl)silacyclobutane (35.5 mg, 0.15 mmol). Compound II-13 was obtained as a colorless oily liquid, 69% yield. 1H NMR (400MHz, CDCl3): δ7.50 (dd, J=2.6, 1.2Hz, 1H), 7.43–7.41 (m, 1H), 7.25–7.24 (m,1H),7.19–7.12(m,3H),7.05–7.01(m,2H),6.99–6.95(m,1H),6.80(dd,J=4.8, 1.1Hz,1H),6.33(s,1H),2.91(td,J=12.3,5.4Hz,1H),2.73–2.68(m,1H),2.10–2 .02(m,1H),1.90–1.80(m,1H),1.11(s,9H),0.92–0.85(m,1H),0.52–0.45(m,1H); 13 C NMR (100MHz, CDCl3): δ167.73,141.38,139.79,138.90,137.29,132.99,132.91,132.21,132.07,129.09,1 28.76,127.33,125.92,124.92,124.41,122.71,39.07,31.60,30.15,25.53,12.64; HRMS(ESI-TOF):calc'd for C 23 H 26 NaS2Si + [M+H + ]417.1137,found417.1136.

[0137] Example 38: Preparation of Compound II-14

[0138]

[0139] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1,1-di(n-butyl)silacyclobutane (27.7 mg, 0.15 mmol). Compound II-14 was obtained as a colorless oily liquid, 71% yield. 1H NMR (400MHz, CDCl3): δ7.20–7.18(m,2H),7.09–7.03(m,2H),5.86(s,1H),2.68–2 .57(m,2H),2.16–2.09(m,1H),1.59–1.49(m,1H),1.36–1.26(m,4H),1.09(s,9H) ,1.04–0.96(m,2H),0.95–0.88(m,5H),0.72(t,J=7.2Hz,3H),0.53–0.49(m,2H), 0.44–0.37(m,1H),0.32–0.25(m,1H),-0.26–-0.33(m,1H),-0.43–-0.50(m,1H); 13 C NMR (100MHz, CDCl3): δ165.14,142.15,141.50,129.78,128.63,127.01,124.23,124.00,38.45,32.65 ,30.22,27.03,27.01,26.42,26.34,26.07,14.10,14.01,13.88,11.51,11.29; HRMS(ESI-TOF):calc'd for C 23 H 38 KSi + [M+K + ]381.2374,found381.2378.

[0140] Example 39: Preparation of Compound II-15

[0141]

[0142] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1,1-dibenzylsilacyclobutane (37.9 mg, 0.15 mmol). Compound II-15 was obtained as a colorless oily liquid, 71% yield. 1H NMR(400MHz, CDCl3): δ7.25–7.19(m,4H),7.16-7.09(m,4H),7.05–6.99(m,4H), 6.78(d,J=7.1Hz,2H),5.94(s,1H),2.62–2.56(m,2H),2.05(dd,J=40.0,12.0Hz, 1H),2.01–1.98(m,1H),1.96–1.87(m,1H),1.67–1.58(m,1H),1.54(d,J=13.8Hz ,1H),1.30(d,J=13.8Hz,1H),1.07(s,9H),0.40–0.33(m,1H),0.18–0.11(m,1H); 13 CNMR (100MHz, CDCl3): δ166.63,141.79,140.64,140.37,139.92,129.54,128.56,128.26,128.10,127.23, 124.32,124.10,124.00,122.78,38.73,31.85,30.08,26.18,23.92,22.47,10.41; HRMS(ESI-TOF):calc'd for C 29 H 34 NaSi + [M+Na + ]433.2322,found433.2331.

[0143] Example 40: Preparation of Compound II-16

[0144]

[0145] The procedure was the same as in Example 25, except that the bromoolefin used was 1-bromo-2-(1-tert-butylvinyl)benzene (23.9 mg, 0.1 mmol) and the silacyclobutane was 1-methyl-1-phenylsilacyclobutane (24.3 mg, 0.15 mmol, 2.5:1 dr). Compound II-16 was obtained as a colorless oily liquid, 71% yield. 1H NMR (400MHz, CDCl3) (mixture of twodiastereoisomers): δ7.56–7.53(m,6H),7.38–7.35(m,9H),7.27(s,2H),7.22–7.17(m,6H),7.16 –7.09(m,6H),7.04–7.01(m,1H),6.96–6.92(m,1H),6.11(s,2.5H),6.06(s,1H),2.95–2.85(m,1H),2. 75–2.69(m,6H),2.32–2.23(m,3H),2.09–1.99(m,1H),1.90–1.81(m,1H),1.68–1.57(m,3H),1.42–1.3 3(m,2H),1.14(s,22H),1.10(s,9H),0.77–0.70(m,2H),0.63–0.59(m,2H),0.28(s,3H),-0.53(s,7H); 13 C NMR(100MHz,CDCl3)(mixture of twodiastereoisomers): δ166.43,141.86,141.74,141.63,140.63,139.71,133 .79,133.39,130.25,129.31,128.83,128.79,128.77,128.47,127.87,127.79, 127.40,127.34,126.99,124.40,124.26,124.19,38.85,38.61,32.73,31.51,3 0.23,30.11,27.19,25.31,13.66,12.36,-2.31,-5.15; HRMS(ESI-TOF):calc'd for C 22 H 28 NaSi + [M+Na + ]343.1852,found343.1856.

[0146] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent replacements and improvements made by any technician familiar with this technical field within the technical scope disclosed by the present invention should be included in the scope of protection of the invention.

Claims

1. A method for preparing a benzosilanol eight-membered ring compound as shown in I (eight-membered arylsilanol) or II (eight-membered alkenylsilanol), characterized in that: The method comprises the following steps: using an o-halostyrene derivative A and a silacyclobutane B as starting materials, reacting in an organic solvent G at 30° C. to 100° C. under a gas protective atmosphere in the presence of a palladium catalyst C, a phosphine ligand D, a base E, and an additive F, stirring the reaction for 1 to 40 hours. After the reaction is complete, the reaction mixture is filtered, extracted, concentrated, and purified to obtain a benzosilacyclopentane octane compound as shown in Formula I or II. The reaction equation is as follows: in: X is iodine or bromine, R 1 -R 5 is one or more of aryl, heteroaryl, alkyl, ester, aldehyde, carbonyl, carboxyl, hydroxyl, mercapto, silyl, amino, cyano, nitro, amide, sulfonyl, alkoxy, alkenyl, alkynyl, halogen, and hydrogen; n represents R 1 The number of groups is 0≤n≤4. When n≥2, the two groups may be the same or different. Ar is an aromatic hydrocarbon or a heterocyclic aromatic hydrocarbon.

2. The method according to claim 1, characterized in that The palladium catalyst is any one or more of Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd(OAc)2, Pd(acac)2, Pd(TFA)2, Pd(OAc)2(PPh3)2, PdCl2(dppf)·DCM, Pd(cod)2Cl2, Pd(PPh3)2Cl2, Pd(MeCN)2Cl2, PdCl2, PdI2, [Pd(allyl)Cl]2, and [Pd(PhC3H4)Cl]2.

3. The method according to claim 1, characterized in that The phosphine ligand is triarylphosphine, trialkylphosphine, dppm, dppe, dppp, dppb, dppf, BINAP, DPEPhos, AmPhos, DavePhos, BrettPhos, MePhos, XPhos, SPhos, AmPhos, RuPhos, XantPhos, t Bu-DavePhos, t Bu-BrettPhos, t Bu-XPhos、Me4 t Bu-Xphos, t Any one or more of Bu-MePhos and JohnPhos.

4. The method according to claim 1, wherein The base is any one or more of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium pivalate, potassium pivalate, cesium pivalate, tripotassium phosphate, potassium formate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide.

5. The method according to claim 1, wherein The additive is any one or more of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, adamantanecarboxylic acid, pivalic acid, acetic acid, and benzoic acid.

6. The method according to claim 1, characterized in that The solvent is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 2-methyltetrahydrofuran, ether, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,3-dioxane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 Saturated alkanes, C 3-12 Fluorinated or chlorinated alkanes, benzene, toluene, xylene, trimethylbenzene, trifluorotoluene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methylpyrrolidone, ethyl acetate, acetonitrile, C 3-12 Any one or more of the saturated alkyl nitriles.

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