Synthesis method of silyl-and methyl-containing alkenylpentanol and derivatives thereof

Abstract

The synthesis method comprises the following steps: sequentially adding a nickel catalyst, a phosphine ligand, a solvent, PhMe2SiBpin, a raw material 2 and a raw material 1 into a reaction container, stirring for 12-30 hours at a specified temperature in a nitrogen or inert gas atmosphere, cooling to 0 DEG C, adding a saturated ammonium chloride solution for quenching reaction, reducing pressure to remove the solvent, filtering, washing, and drying to obtain the silyl and methyl-containing alkene amyl alcohol. And performing column chromatography separation to obtain a target product. The synthesis of the 2-methyl-3-silyl-4-ene pentanol and the derivative thereof and the synthesis of the 2-methyl-5-silyl-3-ene pentanol and the derivative thereof can be realized only through regulation and control of the ligand in the nickel catalyst, and the method is wide in raw material source, convenient to operate, low in production cost and high in safety.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis, and in particular to a method for synthesizing pentyl alcohols and their derivatives containing silicon groups and methyl groups. Background Technology

[0002] Enols containing silicon and methyl groups have wide applications in organic synthesis, such as olefin metathesis, cross-coupling, cycloaddition, and silyl-Prins cyclization, to obtain various cyclic and heterocyclic compounds. They are also used as monomers for the synthesis of silicon-containing polymers. These reactions highlight the importance of enols containing silicon and methyl groups in pharmaceutical synthesis, natural product synthesis, and materials science. Therefore, developing simple and efficient synthetic methods is of great practical value.

[0003]

[0004] Currently, enols containing silicon groups and methyl groups can be synthesized through the following methods:

[0005] 1) It is obtained by the addition of trimethylsilylallyllithium with an epoxide in tetrahydrofuran at -40°C (Schaumann, E.; Kirschning, A. Tetrahedron Lett. 1988, 29, 4281). This reaction has low regioselectivity, requires the allyl metal reagent to be prepared in advance, generates excessive metal waste during the reaction, has low atom economy, and pollutes the environment.

[0006] 2) It is obtained by cross-metathesis reaction of methyl-substituted homoallylic alcohols with allyltrimethylsilane (Engelhardt, FC; Schmitt, MJ; Taylor, REOrg. Lett. 2001, 3, 2209). This method requires the use of the noble metal ruthenium catalyst, and the amount of allyltrimethylsilane used is relatively high, which poses certain risks, and also results in low atom economy and high production costs.

[0007] 3) It is obtained by reacting siloxycycloheptene with methyllithium (Taylor, RE; Engelhardt, FC; Schmitt, MJ; Yuan, HJAm. Chem. Soc. 2001, 123, 2964). This reaction requires the prior preparation of siloxycycloheptene and the use of excess methyllithium, which has certain toxicity and hazards.

[0008] 4) It is obtained by the addition reaction of allyl borate with aldehyde (Peng, F.; Hall, DG J Am. Chem. Soc. 2007, 129, 3070). Allyl borate needs to be prepared in advance, the reaction steps are complicated, and the reaction temperature is very low.

[0009] The reaction equations for the above four synthetic methods are as follows:

[0010]

[0011] In summary, although enols containing silicon and methyl groups are an important class of organic reaction intermediates, existing synthetic methods not only require strict operation and involve complicated steps and high production costs, but also cause certain environmental pollution, making large-scale production face many challenges. Summary of the Invention

[0012] The purpose of this invention is to provide a simple and practical method for synthesizing enols containing silicon and methyl groups and their derivatives. Starting from inexpensive aldehydes, alkyl dienes and silicoboron reagents, the method can achieve highly regioselective synthesis of enols containing silicon and methyl groups in one step by simply controlling the ligands in the nickel catalyst.

[0013] Therefore, the present invention adopts the following technical solution:

[0014] A method for synthesizing enepentyl alcohol and its derivatives containing silicon and methyl groups, the reaction formula and reaction process are as follows:

[0015]

[0016] A nickel catalyst, a phosphine ligand, a solvent, PhMe2Si-Bpin, a compound of formula 2, and a compound of formula 1 are added sequentially to a reaction vessel. The reaction is stirred for 12–30 hours at a specified temperature under a nitrogen or inert gas atmosphere. The mixture is then cooled to 0°C, and a saturated ammonium chloride solution is added to quench the reaction. The solvent is then removed under reduced pressure, and the mixture is separated by column chromatography to obtain a compound of formula 3, wherein the phosphine ligand is triethylphosphine, tributylphosphine, or trioctylphosphine.

[0017] In the above synthesis method, preferably, the nickel catalyst is Ni(COD)2 or Ni( t Bu-stb)3; the solvent is tetrahydrofuran, toluene, mesitylene or n-hexane; the phosphine ligand is triethylphosphine.

[0018] Preferably, the molar ratio of the compound of Formula 1, the nickel catalyst, and the phosphine ligand is 1:(0.05-0.2):(0.06-0.24).

[0019] Preferably, the equivalent ratio of the compound of Formula 1, the compound of Formula 2, and PhMe2Si-Bpin is 1:(1.0 to 2.0):(1.0 to 3.0).

[0020] Preferably, in equations 1 and 3, R 1 They are all alkyl, aryl, or heteroaryl.

[0021] Preferably, the ratio of the compound of Formula 1 to the solvent is 1 mmol: 1 to 5 mL.

[0022] Preferably, the specified temperature is 0–40°C; more preferably, the specified temperature is 20–30°C.

[0023] Preferably, the stirring reaction time is 12-20 hours.

[0024] A nickel-catalyzed method for the synthesis of 2-methyl-5-silyl-3-enpentanol and its derivatives, the reaction formula and reaction process are as follows:

[0025]

[0026] A nickel catalyst, a phosphine ligand, a solvent, PhMe2Si-Bpin, the compound of formula 2, and the compound of formula 1 are added sequentially to a reaction vessel. The reaction is carried out under a nitrogen or inert gas atmosphere and stirred at a specified temperature for 12–30 hours. The mixture is then cooled to 0°C, and the reaction is quenched by adding a saturated ammonium chloride solution. The solvent is removed under reduced pressure, and the mixture is separated by column chromatography to obtain the compound of formula 4. The phosphine ligand is tricyclopentylphosphine, tri-tert-butylphosphine, diphenyl-tert-butylphosphine, dicyclohexylphenylphosphine, dicyclohexyl-tert-butylphosphine, CyJohnPhos, SPhos, XPhos, JohnPhos, RuPhos, or DavePhos.

[0027] Preferably, the nickel catalyst is Ni(COD)2, Ni( t Bu-stb)3 or Ni(COD)(DQ).

[0028] Preferably, the solvent is ethanol, methanol, isopropanol, or tert-butanol.

[0029] Preferably, the phosphine ligand is CyJohnPhos.

[0030] Preferably, the molar ratio of the compound of Formula 1, the nickel catalyst, and the phosphine ligand is 1:(0.025-0.2):(0.03-0.24).

[0031] Preferably, the molar ratio of the compound of Formula 1, the compound of Formula 2, and PhMe2Si-Bpin is 1:(1.0 to 2.0):(1.0 to 3.0).

[0032] Preferably, in equations 1 and 4, R 1 It is alkyl, aryl, or heteroaryl.

[0033] Preferably, the ratio of the compound of Formula 1 to the solvent is 1 mmol: 1 to 5 mL.

[0034] Preferably, the specified temperature is 0–40°C; more preferably, the specified temperature is 20–30°C.

[0035] Preferably, the stirring reaction time is 12-20 hours.

[0036] In the two synthetic methods described above, the compound of Formula 1 is one of the following compounds:

[0037]

[0038]

[0039] This invention starts with alkyl dienes, aldehydes, and silicoboron reagents, and synthesizes high-value-added 2-methyl-3-silyl-4-enpentanol and its derivatives or 2-methyl-5-silyl-3-enpentanol and its derivatives with high regioselectivity in a single step reaction.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] 1. The method of the present invention is simple to operate, and the synthesis of 2-methyl-3-silyl-4-enpentanol and its derivatives or 2-methyl-5-silyl-3-enpentanol and its derivatives is achieved by regulating the organophosphorus ligand in the nickel catalyst alone;

[0042] 2. All reagents used in this invention are commercially available, with a wide range of raw material sources and low prices. Moreover, all reagents are stable at room temperature and pressure, making them easy to handle and requiring no special treatment.

[0043] 3. This invention has been tested at the gram scale, and the reaction is suitable for mass production;

[0044] 4. This invention avoids the use of dangerous reagents such as alkyl metal reagents that are extremely sensitive to air and water, and there are no special requirements for post-processing, which greatly reduces the production cost of synthesizing this type of compound and improves safety. Detailed Implementation

[0045] The technical solution of the present invention will be further described in detail below with reference to the embodiments.

[0046] Example 1

[0047] Synthesis of 3-(dimethyl(phenyl)silyl)-2-methyl-1-(naphthalen-2-yl)pent-4-en-1-ol(3a). The reaction formula is as follows:

[0048]

[0049] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and starting material 1a (15.6 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under an argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding a saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 28.0 mg of colorless liquid, with a yield of 78%. 1 H NMR (400MHz, CDCl3) δ7.80(td,J=8.7,4.4Hz,3H),7.66(s,1H),7.46(q,J=3.7,3.3Hz,4H),7.33(td,J=6.7,3.4Hz,4H),5.98(dt,J=16.9,10.6H z,1H),5.11–4.99(m,2H),4.49(d,J=8.0Hz,1H),2.53(dd,J=11.2,2.3Hz,1H),2.17–2.04(m,2H),0.74(d,J=7.1Hz,3H),0.31(d,J=18.9Hz,6H). 13 C NMR (101MHz, CDCl3) δ141.3,137.9,136.0,134.1,133.2,132.9,129.0,128.1,127.9,127.7,127. 7,126.0,125.7,125.6,124.5,115.6,78.7,39.7,35.4,14.4,-3.6,-3.8.HRMS(ESI)calcd.for[C 24 H 28 NaOSi,M+Na] + :383.1802,found:383.1807.

[0050] Example 2

[0051] Synthesis of Tert-butyl 3-(3-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-4-en-1-yl)-1H-indole-1-carboxylate (3b). The reaction formula and reaction process are as follows:

[0052]

[0053] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting materials 2a (15.0 μL, 0.15 mmol) and 1b (24.5 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography with ethyl acetate / petroleum ether = 1 / 5 as the eluent, yielding 34.1 mg of colorless liquid, with a yield of 76%. 1 H NMR(400MHz, CDCl3)δ8.11(d,J=8.4Hz,1H),7.52–7.47(m,2H),7.46–7.39(m,2H) ,7.37–7.26(m,4H),7.14(t,J=7.5Hz,1H),5.96(dt,J=16.9,10.6Hz,1H),5.13–5. 00(m,2H),4.57(d,J=8.5Hz,1H),2.60(dd,J=11.1,2.3Hz,1H),2.30(tt,J=9.3,5. 9Hz,1H),2.01(s,1H),1.65(s,9H),0.77(d,J=7.1Hz,3H),0.32(d,J=15.6Hz,6H). 13 C NMR (101MHz, CDCl3) δ149.8,137.9,135.9,135.7,134.1,129.0,128.6,127.7,124.4,123.3,123.2, 122.5,120.2,115.7,115.3,83.7,72.3,38.2,35.4,28.2,14.4,-3.6,-3.9.HRMS(ESI)calcd.for[C 27 H 35 [NNaO3Si,M+Na] + :472.2278,found:472.2283.

[0054] Example 3

[0055] Synthesis of 3-(dimethyl(phenyl)silyl)-1-(2-methoxypyridin-4-yl)-2-methylpent-4-en-1-ol(3c). The reaction formula and reaction process are as follows:

[0056]

[0057] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and starting material 1c (13.7 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 11.9 mg of colorless liquid, with a yield of 35%. 1 H NMR (600MHz, CDCl3) δ8.06 (d, J = 5.3 Hz, 1H), 7.43 (d, J = 6.9 Hz, 2H), 7.35 (dd, J = 12.6, 6. 9Hz,3H),6.67(d,J=5.3Hz,1H),6.60(s,1H),5.95(dt,J=16.8,10.6Hz,1H),5.03(dd,J =51.5,13.5Hz,2H),4.30(d,J=7.0Hz,1H),3.93(s,3H),2.32(d,J=11.2Hz,1H),2.13(s ,1H),1.96(t,J=7.4Hz,1H),1.59(s,1H),0.82(d,J=7.1Hz,3H),0.29(d,J=34.7Hz,6H). 13 C NMR (151MHz, CDCl3) δ164.5,155.8,146.7,137.4,136.0,134.0,129.1,127.8,115 .8,114.9,108.4,78.0,53.4,39.2,35.2,14.3,-3.7,-4.0.HRMS(ESI)calcd.for[C 20 H 28 NO2Si,M+H] + :342.1884,found:342.1882.

[0058] Example 4

[0059] Synthesis of 3-(dimethyl(phenyl)silyl)-1-(furan-3-yl)-2-methylpent-4-en-1-ol(3d). The reaction formula and reaction process are as follows:

[0060]

[0061] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (78.6 mg, 0.3 mmol), starting material 2a (15.0 μL, 0.15 mmol), and starting material 1d (9.6 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 25.5 mg of colorless liquid in 85% yield. 1 H NMR (400MHz, CDCl3) δ7.51–7.46(m,2H),7.35(dd,J=4.5,1.9Hz,4H),7.27(s,1H),6.20(s,1H),5.92(dt,J=16.9,10.6Hz,1H),5.04–4.9 3(m,2H),4.34(d,J=7.6Hz,1H),2.43(dd,J=11.2,2.5Hz,1H),1.93(qt,J=7.1,4.2Hz,2H),0.81(d,J=7.1Hz,3H),0.32(d,J=12.9Hz,6H). 13 C NMR (101MHz, CDCl3) δ143.3,139.7,137.8,136.1,134.1,129.1,128.3,127.7,115.4,108.5,71.5,38.8,35.3,14.2,-3.7,-3.8.HRMS(ESI)calcd.for[C 18 H 24 NaO2Si,M+Na] + :323.1438,found:323.1440.

[0062] Example 5

[0063] Synthesis of 3-(dimethyl(phenyl)silyl)-2-methyl-1-(thiophen-3-yl)pent-4-en-1-ol(3e). The reaction formula and reaction process are as follows:

[0064]

[0065] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1e (11.1 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 24.9 mg of colorless liquid, with a yield of 79%. 1 H NMR (400MHz, CDCl3) δ7.51–7.43(m,2H),7.34(dd,J=5.9,1.6Hz,3H),7.25(d,J =4.8Hz,1H),7.08–7.02(m,1H),6.89(dd,J=5.1,1.3Hz,1H),5.93(dt,J=16.9,1 0.6Hz,1H),5.05–4.92(m,2H),4.44(d,J=7.7Hz,1H),2.43(dd,J=11.2,2.4Hz, 1H), 1.99 (qd, J = 7.2, 2.5Hz, 2H), 0.77 (d, J = 7.1Hz, 3H), 0.30 (d, J = 15.4Hz, 6H). 13 C NMR (101MHz, CDCl3) δ145.5,137.9,136.1,134.1,129.0,127.7,125.9,125.8,121.2,115.4,75.0,39.5,35.4,14.2,-3.7,-3.8.HRMS(ESI)calcd.for[C 18 H 24 NaOSSi,M+Na] + :339.1209,found:339.1210.

[0066] Example 6

[0067] Synthesis of 1-cyclohexyl-3-(dimethyl(phenyl)silyl)-2-methylpent-4-en-1-ol(3f). The reaction formula and reaction process are as follows:

[0068]

[0069] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1f (11.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 40 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 23.7 mg of colorless liquid, with a yield of 75%. 1 H NMR(400MHz, CDCl3)δ7.53–7.48(m,2H),7.34(qd,J=4.1,1.4Hz,3H),5.99–5.86(m,1 H),5.02–4.86(m,2H),3.02(q,J=6.4Hz,1H),2.29(dd,J=11.2,2.4Hz,1H),1.83(td, J=7.0,2.3Hz,1H),1.75–1.63(m,4H),1.39–1.29(m,3H),1.21(dd,J=12.6,3.2Hz,1H ),1.17–1.09(m,2H),1.07–0.97(m,2H),0.90(d,J=7.1Hz,3H),0.32(d,J=7.5Hz,6H). 13 CNMR (101MHz, CDCl3) δ138.0,137.0,134.1,129.0,127.7,114.7,80.5,40.4,35 .6,34.6,30.3,26.7,26.6,26.5,26.2,14.5,-3.7,-3.8.HRMS(ESI)calcd.for[C 20 H 32 NaOSi,M+Na] + :339.2115,found:339.2117.

[0070] Example 7

[0071] Synthesis of Tert-butyl 4-(3-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-4-en-1-yl)piperidine-1-carboxylate (3g). The reaction formula and reaction process are as follows:

[0072]

[0073] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (20.0 μL, 0.2 mmol), and 1 g (21.3 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 20.8 mg of colorless liquid, with a yield of 50%. 1 H NMR (400MHz, CDCl3) δ7.53–7.46(m,2H),7.39–7.30(m,3H),5.95(dt,J=16.9,1 0.6Hz,1H),5.04–4.92(m,2H),4.07(s,2H),3.05(s,1H),2.59(s,2H),2.24(dd, J=11.1,2.2Hz,1H),1.80(td,J=6.8,2.3Hz,1H),1.67(dd,J=13.2,3.1Hz,1H), 1.44(s,11H),1.22–1.08(m,3H),0.94(d,J=7.1Hz,3H),0.32(d,J=13.0Hz,6H). 13 C NMR (101MHz, CDCl3) δ154.8,137.7,136.9,134.0,129.1,127.8,115.0,80.2,79 .2,45.8,39.0,35.6,34.3,29.0,28.5,14.6,-3.8,-4.0.HRMS(ESI)calcd.for[C 24 H 39 [NNaO3Si,M+Na] + :440.2591,found:440.2595.

[0074] Example 8

[0075] Synthesis of 3-(dimethyl(phenyl)silyl)-2-methyl-1-(tetrahydro-2H-pyran-4-yl)pent-4-en-1-ol(3h). The reaction formula and reaction process are as follows:

[0076]

[0077] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), and toluene (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1 h (11.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 19.0 mg of colorless liquid, with a yield of 60%. 1 H NMR(400MHz, CDCl3) δ7.50(dd,J=6.8,2.7Hz,2H),7.35(dd,J=5.2,1.9Hz,3H),5.97(dt,J =16.9,10.6Hz,1H),5.04–4.93(m,2H),3.97(dd,J=11.6,4.3Hz,1H),3.92–3.85(m,1H),3 .35–3.27(m,2H),3.04(s,1H),2.24(dd,J=11.1,2.3Hz,1H),1.84–1.78(m,1H),1.67–1.5 4(m,3H),1.37(tq,J=11.9,7.1,5.9Hz,3H),0.96(d,J=7.1Hz,3H),0.32(d,J=12.1Hz,6H). 13 C NMR (101MHz, CDCl3) δ137.8,137.0,134.0,129.1,127.7,114.9,80.4,77.4,77.0,76. 7,68.1,67.8,38.1,35.5,34.0,29.7,27.6,14.7,-3.8,-4.0.HRMS(ESI)calcd.for[C 19 H 30 NaO2Si,M+Na] + :341.1907,found:341.1910.

[0078] Example 9

[0079] Synthesis of Tert-butyl(R)-2-(3-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-4-en-1-yl)pyrrolidine-1-carboxylate(3i). The reaction formula and reaction process are as follows:

[0080]

[0081] Ni(COD)₂ (5.6 mg, 0.02 mmol), PEt₃ (2.8 mg, 0.024 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1i (19.9 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 24.1 mg of colorless liquid in 60% yield (containing diastereomer dr = 6:1). 1 H NMR (400MHz, CDCl3) δ7.52 (dd, J=6.5, 3.0Hz, 2H), 7.34 (dd, J=4.9, 2.0Hz, 3H), 5.80(s,1H),4.97(dd,J=30.5,13.5Hz,2H),3.81(d,J=10.1Hz,3H),3.52(s,1H) ,3.24(td,J=7.1,3.9Hz,1H),2.56–2.43(m,1H),1.90–1.84(m,2H),1.69(ddd, J=13.7,7.0,2.8Hz,3H),1.43(s,9H),0.90–0.80(m,3H),0.32(d,J=1.9Hz,6H). 13 C NMR (101MHz, CDCl3) δ155.3,138.2,134.1,133.6,128.9,127.6,115.4,79.4,74.0, 59.6,47.5,36.0,35.6,28.5,28.4,24.5,13.9,-3.5,-3.6.HRMS(ESI)calcd.for[C 23 H 37 [NNaO3Si,M+Na] + :426.2435,found:426.2438.

[0082] Example 10

[0083] Synthesis of 1-cyclobutyl-3-(dimethyl(phenyl)silyl)-2-methylpent-4-en-1-ol(3j). The reaction formula and reaction process are as follows:

[0084]

[0085] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1j (8.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under nitrogen atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 19.0 mg of colorless liquid, with a yield of 66%. 1 H NMR (400MHz, CDCl3) δ7.49 (dd, J=5.6, 2.3Hz, 2H), 7.34 (dd, J=5.0, 1.7Hz, 3H) ,5.92(dt,J=18.2,10.6Hz,1H),5.01–4.89(m,2H),3.21(t,J=6.7Hz,1H),2.4 5–2.36(m,1H),2.26(d,J=11.4Hz,1H),1.97–1.90(m,1H),1.86–1.75(m,3H), 1.73–1.62(m,3H),1.42(s,1H),0.88(d,J=7.2Hz,3H),0.30(d,J=10.0Hz,6H). 13 C NMR(101MHz, CDCl3)δ138.0,137.0,134.0,129.0,127.7,114.5,114.5,80.2,39.7,36.4,35.9,25.1,24.5,18.2,14.5,-3.7,-3.9.HRMS(ESI)calcd.for[C 18 H 28 NaOSi,M+Na] + :311.1802,found:311.1802.

[0086] Example 11

[0087] Synthesis of 1-cyclopropyl-3-(dimethyl(phenyl)silyl)-2-methylpent-4-en-1-ol(3k). The reaction formula and reaction process are as follows:

[0088]

[0089] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1k (7.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 15.9 mg of colorless liquid, with a yield of 58%. 1 H NMR(400MHz, CDCl3)δ7.56–7.48(m,2H),7.34(dt,J=5.5,1.9Hz,3H),5.93–5.65( m,1H),5.00–4.80(m,2H),2.58(t,J=8.1Hz,1H),2.45(dd,J=11.2,2.6Hz,1H),1.8 5(pd,J=7.3,2.4Hz,1H),1.52(s,1H),0.93(dd,J=15.0,6.9Hz,3H),0.79(qt,J=8 .3,4.8Hz,1H),0.54–0.40(m,2H),0.32(dd,J=8.9,3.1Hz,6H),0.27–0.13(m,2H). 13 C NMR(101MHz, CDCl3)δ136.2,134.2,132.2,127.0,125.7,112.9,78.1,37.9,34.1,14.6,12.2,2.3,-0.0,-5.5,-5.7.HRMS(ESI)calcd.for[C 17 H 26 NaOSi,M+Na] + :297.1645,found:297.1644.

[0090] Example 12

[0091] Synthesis of 5-(dimethyl(phenyl)silyl)-2,4-dimethylhept-6-en-3-ol(3l). The reaction formula and reaction process are as follows:

[0092]

[0093] Ni(COD)₂ (2.8 mg, 0.01 mmol), PBu₃ (2.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1 L (7.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 13.2 mg of colorless liquid, with a yield of 48%. 1 H NMR (400MHz, CDCl3) δ7.53–7.49(m,2H),7.34(dd,J=5.1,2.0Hz,3H),5.92(dt,J=16.8,10.6Hz,1H),5.01–4.88(m,2H),3.02(t,J=6.0Hz ,1H),2.33(dd,J=11.2,2.4Hz,1H),1.81–1.68(m,2H),1.33(s,1H),0.89(d,J=7.2Hz,3H),0.83(d,J=6.9Hz,6H),0.32(d,J=5.6Hz,6H). 13 C NMR(101MHz, CDCl3)δ138.0,136.9,134.1,129.0,127.7,114.8,80.8,35.7,35.4,30.2,20.1,16.1,14.4,-3.7.HRMS(ESI)calcd.for[C 17 H 28 NaOSi,M+Na] + :299.1802,found:299.1802.

[0094] Example 13

[0095] Synthesis of 5-(dimethyl(phenyl)silyl)-4-methyl-1-phenylhept-6-en-3-ol(3m). The reaction formula and reaction process are as follows:

[0096]

[0097] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1m (13.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 20.9 mg of colorless liquid, with a yield of 62%. 1 H NMR (400MHz, CDCl3) δ7.50 (dd, J=6.4, 2.9Hz, 2H), 7.34 (dd, J=5.1, 2.0Hz, 3H), 7.25 (d, J=7.5Hz, 2 H),7.15(dd,J=6.7,5.0Hz,3H),5.90(dt,J=16.9,10.6Hz,1H),5.00–4.90(m,2H),3.35(ddd,J=9.4 ,6.5,3.1Hz,1H),2.77(ddd,J=13.7,10.5,5.2Hz,1H),2.55–2.47(m,1H),2.29(dd,J=11.2,3.1Hz, 1H),1.75–1.66(m,2H),1.62(dt,J=9.4,4.7Hz,2H),0.90(d,J=7.1Hz,3H),0.31(d,J=12.3Hz,6H). 13 C NMR (151MHz, CDCl3) δ142.5,137.9,136.8,134.0,129.1,128.4,128.4,127.8,125 .7,114.8,75.9,38.6,36.7,36.1,32.4,14.2,-3.6,-3.9.HRMS(ESI)calcd.for[C 22 H 30 NaOSi,M+Na] + :361.1958,found:361.1962.

[0098] Example 14

[0099] Synthesis of 1-((Tert-butyldimethylsilyl)oxy)-6-(dimethyl(phenyl)silyl)-5-methyloct-7-en-4-ol(3n). The reaction formula and reaction process are as follows:

[0100]

[0101] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1n (20.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 27.2 mg of colorless liquid, with a yield of 67%. 1 H NMR (400MHz, CDCl3) δ7.51 (dd, J=6.6, 3.0Hz, 2H), 7.34 (dd, J=5.0, 1.9Hz, 3H), 5.92–5.79 (m, 1H),4.98–4.89(m,2H),3.60(td,J=5.4,2.2Hz,2H),3.32(t,J=8.1Hz,1H),2.33(dd,J=11.1, 3.1Hz,1H),2.22(s,1H),1.68(ddt,J=10.2,7.2,2.9Hz,2H),1.57(ddd,J=10.9,6.7,2.5Hz,2 H),1.35–1.29(m,1H),0.89(s,9H),0.87(d,J=7.1Hz,3H),0.31(d,J=9.3Hz,6H),0.04(s,6H). 13 C NMR (101MHz, CDCl3) δ138.2,136.6,134.1,128.9,127.7,114.7,75.3,63.4,38.5, 36.1,31.4,29.1,26.0,18.3,14.0,-3.5,-3.9,-5.3,-5.3.HRMS(ESI)calcd.for[C 23 H 42 NaO2Si2,M+Na] + :429.2616,found:429.2616.

[0102] Example 15

[0103] Synthesis of 9-chloro-3-(dimethyl(phenyl)silyl)-4-methylnon-1-en-5-ol(3o). The reaction formula and reaction process are as follows:

[0104]

[0105] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1o (12.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 23.0 mg of colorless liquid, with a yield of 71%. 1 H NMR (400MHz, CDCl3) δ7.52–7.48(m,2H),7.35–7.31(m,3H),5.88(dt,J=16.9,10.6Hz,1H ),5.00–4.89(m,2H),3.47(t,J=6.7Hz,2H),3.28(d,J=6.0Hz,1H),2.27(dd,J=11.1,3.1 Hz,1H),1.77–1.69(m,2H),1.65(td,J=7.1,3.2Hz,2H),1.57–1.48(m,1H),1.42(ddt,J= 11.5,7.0,3.6Hz,1H),1.35–1.25(m,2H),0.89(d,J=7.1Hz,3H),0.31(d,J=12.1Hz,6H). 13 C NMR(101MHz, CDCl3)δ137.9,136.7,134.0,129.0,127.7,114.8,76.1,45.0,38.4,36.0,33.8,32.7,23.4,14.2,-3.6,-4.0.HRMS(ESI)calcd.for[C 18 H 29 ClNaOSi,M+Na] + :347.1568,found:347.1570.

[0106] Example 16

[0107] Synthesis of 7-(dimethyl(phenyl)silyl)-6-methylnon-8-ene-1,5-diol(3p). The reaction formula and reaction process are as follows:

[0108]

[0109] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1p (10.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 8.8 mg of colorless liquid, with a yield of 29%. 1 H NMR (400MHz, CDCl3) δ7.53–7.47(m,2H),7.35(t,J=3.3Hz,3H),5.82(m,1H),4.94(m,2H),3.60(t,J=6.0Hz,2H),3.47–3.19(m,1H),2.28 (dd,J=11.1,3.1Hz,1H),1.66(t,J=5.5Hz,3H),1.55–1.42(m,4H),1.29(d,J=10.1Hz,2H),0.89(d,J=7.1Hz,3H),0.31(d,J=11.6Hz,6H). 13 C NMR(101MHz, CDCl3)δ136.7,134.0,133.9,129.0,127.7,114.7,76.1,62.8,38.5,36.1,34.2,32.7,22.1,14.2,-3.6,-3.9.HRMS(ESI)calcd.for[C 18 H 30 NaO2Si,M+Na] + :329.1907,found:329.1909.

[0110] Example 17

[0111] Synthesis of 3-(dimethyl(phenyl)silyl)-4-methyl-9-(trimethylsilyl)non-1-en-8-yn-5-ol(3q). The reaction formula and reaction process are as follows:

[0112]

[0113] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1q (15.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 24.0 mg of colorless liquid, with a yield of 50%. 1 H NMR (400MHz, CDCl3) δ7.54–7.51(m,2H),7.37(t,J=2.8Hz,3H),5.89(dt,J= 16.9,10.5Hz,1H),5.03–4.92(m,2H),3.43(d,J=8.0Hz,1H),2.35–2.29(m,2 H),2.24(dd,J=17.0,7.6Hz,1H),1.76(d,J=5.4Hz,1H),1.72–1.67(m,2H),1 .52–1.46(m,1H),0.90(d,J=7.1Hz,3H),0.34(d,J=9.5Hz,6H),0.15(s,9H). 13 C NMR(101MHz, CDCl3)δ137.8,136.3,133.9,128.9,127.6,114.8,107.3,84.7,75.0,38.3,36.0,33.2,16.6,13.9,-0.0,-3.7,-4.0.HRMS(ESI)calcd.for[C 21 H 34 NaOSi2,M+Na] + :381.2040,found:381.2042.

[0114] Example 18

[0115] Synthesis of (E)-6-(dimethyl(phenyl)silyl)-3,5-dimethylocta-2,7-dien-4-ol(3r). The reaction formula and reaction process are as follows:

[0116]

[0117] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1r (13.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 10.0 mg of colorless liquid in 35% yield. 1 H NMR (400MHz, CDCl3) δ7.7(t,J=8.1Hz,2H),7.3–7.2(m,4H),7.2–7.1(m,1H),7.1–7.1(m,2H),4.7–4.6(m,1H),3.3–3.2(m,1H),2.6–2.4(m ,2H),2.4(d,J=8.3Hz,3H),1.6(tq,J=10.4,5.1Hz,2H),1.3–1.3(m,2H),1.2–1.1(m,3H),0.8(dd,J=6.7,3.4Hz,3H),0.7(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.2,136.8,135.9,134.1,128.9,127.6,122.0,115.2,81.5 ,77.3,77.0,76.7,35.3,35.0,14.0,13.0,10.8,-3.7,-3.7.HRMS(ESI)calcd.for[C 18 H 28 NaOSi,M+Na] + :311.1802,found:311.1802.

[0118] Example 19

[0119] Synthesis of 1-([1,1'-biphenyl]-4-yl)-3-(dimethyl(phenyl)silyl)pent-4-en-1-ol(3s). The reaction formula and reaction process are as follows:

[0120]

[0121] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2b (8.1 mg, 0.15 mmol), and 1s (18.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 24.1 mg of colorless liquid, with a yield of 65%. 1 H NMR (400MHz, CDCl3) δ7.58(s,1H),7.56–7.51(m,3H),7.51–7.46(m,2H),7.42(dd,J=8.4,6.9Hz,2H),7.36–7.29(m,6H),5.70(dt,J=17.1,10.0H z,1H),5.06–4.92(m,2H),4.75(dd,J=9.7,2.8Hz,1H),2.25(ddd,J=12.5 ,9.6,3.0Hz,1H),1.84–1.69(m,2H),1.59(s,1H),0.29(d,J=3.0Hz,6H). 13 C NMR (101MHz, CDCl3) δ144.4,140.9,140.2,139.0,137.2,134.1,129.1,128.8,127.7,1 27.3,127.2,127.1,126.1,113.7,72.0,38.3,30.7,-4.5,-5.2.HRMS(ESI)calcd.for[C 25 H 28 NaOSi,M+Na] + :395.1802,found:395.1803.

[0122] Example 20

[0123] Synthesis of (7S)-3-(dimethyl(phenyl)silyl)-4,7,11-trimethyldodeca-1,10-dien-5-ol(3t). The reaction formula and reaction process are as follows:

[0124]

[0125] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1t (15.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent (1 / 10) to give 20.0 mg of colorless liquid in 56% yield (containing diastereomer dr = 1:1). 1 H NMR (400MHz, CDCl3) δ7.50 (dd, J=5.2, 2.5Hz, 2H), 7.34 (dd, J=5.1, 1.9Hz, 3H), 6.00–5.83 (m, 1H),5.08(s,1H),5.00–4.89(m,2H),3.43–3.34(m,1H),2.32(td,J=11.2,2.8Hz,1H),1.96(td ,J=14.3,7.1Hz,2H),1.67(d,J=4.3Hz,3H),1.59(d,J=4.0Hz,6H),1.41–1.29(m,2H),1.16(d dt,J=14.0,10.0,3.1Hz,2H),0.91–0.87(m,4H),0.83(d,J=6.6Hz,2H),0.31(d,J=8.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ138.0,136.9,136.7,134.1,134.0,131.1,129.0,127.7,127.7,124.9,124.9,114.6,114.6,74.7,73.9,42.7,42.3,39 .1,38.6,38.2,36.3,36.1,35.9,29.5,29.1,25.7,25.6,25.4,20.6,19.1,17.7,14.3,14.2,-3.6,-3.7,-3.8,-3.9.HRMS(ESI)calcd.for[C 23 H 38 NaOSi,M+Na] + :381.2584,found:381.2586.

[0126] Example 21

[0127] Synthesis of 3-(dimethyl(phenyl)silyl)-2-methyl-1-((R)-4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)pent-4-en-1-ol(3u). The reaction formula and reaction process are as follows:

[0128]

[0129] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), tetrahydrofuran (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1u (15.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent (1 / 10) to give 18.0 mg of colorless liquid in 51% yield (containing diastereomer dr = 1:1). 1 H NMR (400MHz, CDCl3) δ7.53–7.48(m,2H),7.37–7.31(m,3H),5.87(dtd,J=17.4,10.5,8.3Hz,1H) ,5.59(s,1H),5.04–4.90(m,2H),4.71(d,J=11.6Hz,2H),3.65(t,J=7.4Hz,1H),2.36(ddd,J=14 .5,11.1,2.4Hz,1H),2.12(dd,J=15.0,5.6Hz,2H),2.00–1.92(m,1H),1.87–1.76(m,3H),1.73( s,3H),1.58(s,2H),1.41(dt,J=10.5,4.6Hz,1H),0.78(t,J=6.4Hz,3H),0.31(d,J=8.0Hz,6H). 13C NMR (101MHz, CDCl3) δ149.8,149.8,138.6,138.5,138.1,136.4,136.0,13 4.1,129.0,128.9,127.7,127.6,123.9,123.4,115.2,115.2,108.6,108.6 ,80.7,80.0,41.2,41.2,35.3,35.3,35.0,30.5,30.4,27.5,27.4,24.0,23 .5,20.8,20.8,14.2,14.0,-3.7,-3.7,-3.8,-3.8.HRMS(ESI)calcd.for[C 23 H 34 NaOSi,M+Na] + :377.2271,found:377.2273.

[0130] Example 22

[0131] Synthesis of 9-chloro-3-(dimethyl(phenyl)silyl)-4-methylnon-1-en-5-ol(3o). The reaction formula and reaction process are as follows:

[0132]

[0133] Ni ( t Bu-stb)3 (280 mg, 0.3 mmol), PEt3 (42.5 mg, 0.36 mmol), tetrahydrofuran (30 mL), PhMe2SiBpin (3144 mg, 12 mmol), starting material 2a (612.5 mg, 9 mmol), 1o (720.2 mg, 6 mmol), reacted at 25 °C under argon atmosphere for 30 hours, then cooled to 0 °C, the reaction was quenched by adding saturated ammonium chloride solution, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography with ethyl acetate / petroleum ether = 1 / 10 as the eluent, yielding 1.32 g of colorless liquid, with a yield of 68%. 1H NMR (400MHz, CDCl3) δ7.52–7.48(m,2H),7.35–7.31(m,3H),5.88(dt,J=16.9,10.6Hz,1H ),5.00–4.89(m,2H),3.47(t,J=6.7Hz,2H),3.28(d,J=6.0Hz,1H),2.27(dd,J=11.1,3.1 Hz,1H),1.77–1.69(m,2H),1.65(td,J=7.1,3.2Hz,2H),1.57–1.48(m,1H),1.42(ddt,J= 11.5,7.0,3.6Hz,1H),1.35–1.25(m,2H),0.89(d,J=7.1Hz,3H),0.31(d,J=12.1Hz,6H). 13 C NMR(101MHz, CDCl3)δ137.9,136.7,134.0,129.0,127.7,114.8,76.1,45.0,38.4,36.0,33.8,32.7,23.4,14.2,-3.6,-4.0.HRMS(ESI)calcd.for[C 18 H 29 ClNaOSi,M+Na] + :347.1568,found:347.1570.

[0134] Example 23

[0135] Synthesis of (E)-5-(dimethyl(phenyl)silyl)-2-methyl-1-(naphthalen-2-yl)pent-3-en-1-ol(4a). The reaction formula and reaction process are as follows:

[0136]

[0137] Ni(COD)₂ (2.8 mg, 0.01 mmol), PEt₃ (1.4 mg, 0.012 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and starting material 1a (15.6 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 30.9 mg of colorless liquid, with a yield of 86%. 1H NMR (400MHz, CDCl3) δ7.82–7.76(m,3H),7.71(s,1H),7.52–7.41(m,5H),7.37–7.30(m,3H),5.62(dt,J=15.6,8.0Hz,1H),5.18(dd,J=15.2 ,8.5Hz,1H),4.34(d,J=8.0Hz,1H),2.45(q,J=7.5Hz,1H),2.20(s,1H),1.75(d,J=8.0Hz,2H),0.81(d,J=6.8Hz,3H),0.29(d,J=5.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ140.1,138.4,134.1,133.6,133.2,133.1,131.1,129.4,129.2,128.0,127. 9,127.7,126.0,126.0,125.7,124.8,78.2,45.9,22.3,17.5,-3.3,-3.4.HRMS(ESI)calcd.for[C 24 H 28 NaOSi,M+Na] + :383.1802,found:383.1803.

[0138] Example 24

[0139] Synthesis of Tert-butyl-((E)-5-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-3-en-1-yl)-1H-indole-1-carboxylate (4b). The reaction formula and reaction process are as follows:

[0140]

[0141] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting materials 2a (15.0 μL, 0.15 mmol) and 1b (24.5 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 42.6 mg of colorless liquid, with a yield of 95%. 1H NMR (400MHz, CDCl3) δ8.14(d,J=8.4Hz,1H),7.64(d,J=7.8Hz,1H),7.52–7.46( m,3H),7.38–7.29(m,4H),7.25–7.19(m,1H),5.61(dt,J=15.6,8.0Hz,1H),5.2 0(dd,J=15.2,8.5Hz,1H),4.48(d,J=7.9Hz,1H),2.66(h,J=7.2Hz,1H),2.08(s ,1H),1.73(s,1H),1.66(s,10H),0.89(d,J=6.8Hz,3H),0.28(d,J=9.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ138.4,134.1,133.6,131.0,129.4,129.1,129.0,127.9,127.7,124.4,123.5, 122.5,122.2,120.3,115.3,83.6,71.8,44.4,28.2,22.3,17.8,-3.3,-3.5.HRMS(ESI)calcd.for[C 27 H 35 [NNaO3Si,M+Na] + :472.2278,found:472.2285.

[0142] Example 25

[0143] Synthesis of (E)-5-(dimethyl(phenyl)silyl)-1-(2-methoxypyridin-4-yl)-2-methylpent-3-en-1-ol(4c). The reaction formula and reaction process are as follows:

[0144]

[0145] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1c (13.7 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 19.1 mg of colorless liquid, with a yield of 56%. 1H NMR (400MHz, CDCl3) δ8.08 (d, J=5.3Hz, 1H), 7.51–7.45 (m, 2H), 7.37 (dd, J=4.6, 2. 0Hz,3H),6.77(dd,J=5.3,1.5Hz,1H),6.65(d,J=1.3Hz,1H),5.60–5.49(m,1H),5.0 7(dd,J=15.3,8.4Hz,1H),4.15(d,J=7.3Hz,1H),3.92(s,3H),2.32(q,J=7.2Hz,1H ), 2.08 (s, 1H), 1.73 (d, J = 8.0Hz, 3H), 0.86 (d, J = 6.9Hz, 3H), 0.27 (d, J = 4.5Hz, 6H). 13 C NMR (101MHz, CDCl3) δ164.4,154.5,146.6,138.2,133.6,130.0,129.7,129.2,127 .9,115.2,108.8,76.6,53.4,45.2,22.3,17.1,-3.3,-3.5.HRMS(ESI)calcd.for[C 20 H 28 NO2Si,M+H] + :342.1884,found:342.1883.

[0146] Example 26

[0147] Synthesis of (E)-5-(dimethyl(phenyl)silyl)-1-(furan-3-yl)-2-methylpent-3-en-1-ol(4d). The reaction formula and reaction process are as follows:

[0148]

[0149] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (26.2 mg, 0.1 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1d (9.6 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 22.2 mg of colorless liquid, with a yield of 74%. 1H NMR (400MHz, CDCl3) δ7.49 (dd, J=6.6, 2.9Hz, 2H), 7.37 (d, J=2.6Hz, 4H), 7.32 (s, 1H), 6.34 (s, 1H), 5.58 (dt, J=15.7, 8.0Hz, 1H), 5.18–5. 05(m,1H),4.20(d,J=7.7Hz,1H),2.33(h,J=7.2Hz,1H),1.93(s,1H),1.73(d,J=8.0Hz,2H),0.86(d,J=6.8Hz,3H),0.28(d,J=2.8Hz,6H). 13 C NMR (101MHz, CDCl3) δ143.1,140.0,138.3,133.6,130.7,129.3,129.1,127.9,126.9,108.7,70.5,44.6,22.3,17.2,-3.3,-3.5.HRMS(ESI)calcd.for[C 18 H 24 NaO2Si,M+Na] + :323.1438,found:323.1438.

[0150] Example 27

[0151] Synthesis of (E)-5-(dimethyl(phenyl)silyl)-2-methyl-1-(thiophen-3-yl)pent-3-en-1-ol(4e). The reaction formula and reaction process are as follows:

[0152]

[0153] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1e (11.1 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 0 °C under argon atmosphere for 12 hours. Then, a saturated ammonium chloride solution was added to quench the reaction. The solvent was removed under reduced pressure, and the mixture was separated by column chromatography with ethyl acetate / petroleum ether = 1 / 10 as the eluent, yielding 23.0 mg of colorless liquid, with a yield of 73%. 1H NMR (400MHz, CDCl3) δ7.51–7.45(m,2H),7.39–7.33(m,3H),7.25(dd,J=5.2,3.2Hz ,1H),7.09(dd,J=3.1,1.2Hz,1H),7.01(dd,J=5.0,1.3Hz,1H),5.57(dt,J=15.6,8. 0Hz,1H),5.13(dd,J=15.2,8.4Hz,1H),4.32(d,J=7.7Hz,1H),2.37(p,J=7.3Hz,1H ), 2.02 (s, 1H), 1.73 (d, J = 8.0Hz, 2H), 0.83 (d, J = 6.8Hz, 3H), 0.28 (d, J = 2.8Hz, 6H). 13 C NMR (101MHz, CDCl3) δ144.1,138.4,134.1,133.6,130.9,129.1,127.9,126.0,125.6,121.6,74.2,45.3,22.3,17.2,-3.3,-3.4.HRMS(ESI)calcd.for[C 18 H 24 NaOSSi,M+Na] + :339.1209,found:339.1211.

[0154] Example 28

[0155] Synthesis of (E)-1-cyclohexyl-5-(dimethyl(phenyl)silyl)-2-methylpent-3-en-1-ol(4f). The reaction formula and reaction process are as follows:

[0156]

[0157] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (10.0 μL, 0.1 mmol), and 1f (10.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 22.4 mg of colorless liquid, with a yield of 71%. 1H NMR (400MHz, CDCl3) δ7.52–7.48(m,2H),7.35(dd,J=4.2,2.1Hz,3H),5.46(dt,J=15.6,8.0Hz,1H),5.15(dd,J=15.3,8.4Hz,1H),2.96(q,J =5.4Hz,1H),2.27(dt,J=14.4,7.0Hz,1H),1.81–1.53(m,8H),1.26(d,J=5.0Hz,2H),1.18–1.01(m,4H),0.95(d,J=6.8Hz,3H),0.28(s,6H). 13 C NMR (101MHz, CDCl3) δ138.6,133.6,130.8,129.0,127.8,127.8,79.1,40.3,39. 7,30.0,27.1,26.6,26.5,26.2,22.1,17.8,-3.3,-3.3.HRMS(ESI)calcd.for[C 20 H 32 NaOSi,M+Na] + :339.2115,found:339.2115.

[0158] Example 29

[0159] Synthesis of Tert-butyl-((E)-5-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-3-en-1-yl)piperidine-1-carboxylate (4g). The reaction formula and reaction process are as follows:

[0160]

[0161] Ni(COD)₂ (5.6 mg, 0.02 mmol), CyJohnPhos (8.4 mg, 0.024 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1 g (21.3 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 17.9 mg of colorless liquid, with a yield of 43%. 1H NMR (400MHz, CDCl3) δ7.49 (dd, J=6.5, 3.0Hz, 2H), 7.35 (dd, J=4.2, 2.1Hz, 3H), 5.46 (dt, J=15.6, 7.9Hz,1H),5.14(ddt,J=15.2,8.4,1.3Hz,1H),4.11(s,2H),2.99(t,J=5.7Hz,1H),2.59(s,2H),2 .25(p,J=6.8Hz,1H),1.72(d,J=8.0Hz,2H),1.71–1.65(m,1H),1.49(d,J=17.2Hz,2H),1.45(s,9 H),1.36(ddt,J=13.4,7.5,3.6Hz,2H),1.31(d,J=4.3Hz,1H),0.97(d,J=6.8Hz,3H),0.28(s,6H). 13 C NMR(101MHz, CDCl3)δ154.8,138.4,134.0,133.6,130.0,129.1,128.3,127.8,79.2,78.2,39.6,38.9,28.8,28.5,22.1,17.8,-3.3.HRMS(ESI)calcd.for[C 24 H 39 [NNaO3Si,M+Na] + :440.2591,found:440.2596.

[0162] Example 30

[0163] Synthesis of (E)-5-(dimethyl(phenyl)silyl)-2-methyl-1-(tetrahydro-2H-pyran-4-yl)pent-3-en-1-ol(4h). The reaction formula and reaction process are as follows:

[0164]

[0165] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and ethanol (11.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours. The mixture was then cooled to 0 °C, and the reaction was quenched by adding saturated ammonium chloride solution. The solvent was removed under reduced pressure, and the mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 20.0 mg of colorless liquid in 63% yield. 1 H NMR(400MHz, CDCl3)δ7.49(dd,J=6.5,3.1Hz,2H),7.39–7.29(m,3H),5.46(dt,J=15.6, 7.9Hz,1H),5.16(dd,J=15.3,8.4Hz,1H),4.05–3.93(m,2H),3.31(ddq,J=13.7,10.8,4 .3,3.4Hz,2H),3.00(t,J=5.2Hz,1H),2.25(h,J=6.9Hz,1H),1.72(d,J=8.0Hz,2H),1.6 4(d,J=12.9Hz,1H),1.50–1.38(m,4H),1.30(s,1H),0.99(d,J=6.9Hz,3H),0.28(s,6H). 13 C NMR (101MHz, CDCl3) δ138.5,133.6,129.8,129.1,128.2,127.8,78.5,68.1,67.8,39.1,38.1,29.5,28.1,22.1,17.9,-3.3,-3.3.HRMS(ESI)calcd.for[C 19 H 30 NaO2Si,M+Na] + :341.1907,found:341.1910.

[0166] Example 31

[0167] Synthesis of Tert-butyl(R)-2-((E)-5-(dimethyl(phenyl)silyl)-1-hydroxy-2-methylpent-3-en-1-yl)pyrrolidine-1-carboxylate(4i). The reaction formula and reaction process are as follows:

[0168]

[0169] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1i (19.9 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 16.9 mg of colorless liquid in 42% yield (containing diastereomer dr = 5:1). 1 H NMR(400MHz, CDCl3)δ7.50(dd,J=6.5,3.2Hz,2H),7.35(dd,J=4.3,2.1Hz,3H),5.54–5.40(m,1H),5.21(s,1H),3.91(d,J=48.0Hz,1H),3.75–3.40(m ,2H),3.27(s,1H),2.08(d,J=7.8Hz,1H),1.91(t,J=6.4Hz,3H),1.78(d,J =6.7Hz,1H),1.70(d,J=7.9Hz,3H),1.46(s,9H),0.98(s,3H),0.28(s,6H). 13 C NMR (101MHz, CDCl3) δ155.6,138.5,133.6,131.8,129.0,127.8,127.2,79.3,74.8, 59.7,47.5,41.0,28.6,25.0,24.6,22.0,18.0,-3.3,-3.4.HRMS(ESI)calcd.for[C 23 H 37 [NNaO3Si,M+Na] + :426.2435,found:426.2435.

[0170] Example 32

[0171] Synthesis of (E)-1-cyclobutyl-5-(dimethyl(phenyl)silyl)-2-methylpent-3-en-1-ol(4j). The reaction formula and reaction process are as follows:

[0172]

[0173] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), methanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and starting material 1j (8.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under nitrogen atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 23.0 mg of colorless liquid in 80% yield. 1 H NMR(400MHz, CDCl3) δ7.50(dd,J=6.4,3.1Hz,2H),7.38–7.32(m,3H),5.41(dt,J=15.6,7.9Hz,1H),5.12(dd,J=15.3,8.6Hz,1H),3.17(dd,J=7.6,5.2Hz, 1H),2.35–2.24(m,1H),2.04(dt,J=13.6,7.0Hz,1H),1.93–1.74(m,6H),1.7 0(d,J=7.9Hz,2H),1.30(s,1H),0.94(d,J=7.0Hz,3H),0.28(d,J=1.9Hz,6H). 13 C NMR(101MHz, CDCl3)δ138.6,133.6,130.7,129.0,127.8,127.6,78.8,41.1,39.3,25.0,24.5,22.1,18.2,17.5,-3.3,-3.4.HRMS(ESI)calcd.for[C 18 H 28 NaOSi,M+Na] + :311.1802,found:311.1801.

[0174] Example 33

[0175] Synthesis of (E)-1-cyclopropyl-5-(dimethyl(phenyl)silyl)-2-methylpent-3-en-1-ol(4k). The reaction formula and reaction process are as follows:

[0176]

[0177] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1k (7.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 21.1 mg of colorless liquid, with a yield of 77%. 1 H NMR (400MHz, CDCl3) δ7.52–7.45(m,2H),7.35(dd,J=4.4,2.1Hz,3H),5.50(dt,J=15.5,7. 9Hz,1H),5.20(dd,J=15.2,8.6Hz,1H),2.53(dd,J=8.6,6.4Hz,1H),2.25(dq,J=13.5,7.0 Hz,1H),1.71(d,J=7.9Hz,2H),1.62(s,1H),1.03(d,J=6.9Hz,3H),0.78(ddt,J=13.3,8.3 ,4.1Hz,1H),0.48(tdd,J=8.2,5.1,3.8Hz,2H),0.28(d,J=2.1Hz,6H),0.26–0.13(m,2H). 13 C NMR(101MHz, CDCl3)δ138.7,133.7,131.6,129.1,127.9,127.9,80.1,44.8,22.1,17.6,15.5,3.5,2.1,-3.2,-3.3.HRMS(ESI)calcd.for[C 17 H 26 NaOSi,M+Na] + :297.1645,found:297.1648.

[0178] Example 34

[0179] Synthesis of (E)-7-(dimethyl(phenyl)silyl)-2,4-dimethylhept-5-en-3-ol(4l). The reaction formula and reaction process are as follows:

[0180]

[0181] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1 L (7.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 22.0 mg of colorless liquid in 80% yield. 1 H NMR (400MHz, CDCl3) δ7.55–7.44(m,2H),7.44–7.29(m,3H),5.47(dt,J=15.6,8.0Hz,1H),5.15(dd,J=15.3,8.6Hz,1H),2.96(t,J=5.9Hz,1H),2 .21(h,J=7.0Hz,1H),1.71(d,J=8.0Hz,2H),1.62(q,J=6.4Hz,1H),1.32(s,1H),0.93(dd,J=9.5,6.8Hz,6H),0.87(d,J=6.7Hz,3H),0.28(s,6H). 13 C NMR(101MHz, CDCl3)δ138.5,133.6,131.0,129.0,127.9,127.8,79.6,40.6,30.3,22.1,20.0,17.7,16.4,-3.3,-3.4.HRMS(ESI)calcd.for[C 17 H 28 NaOSi,M+Na] + :299.1802,found:299.1802.

[0182] Example 35

[0183] Synthesis of (E)-7-(dimethyl(phenyl)silyl)-4-methyl-1-phenylhept-5-en-3-ol(4m). The reaction formula and reaction process are as follows:

[0184]

[0185] Ni(COD)₂ (1.4 mg, 0.005 mmol), DavePhos (2.4 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1m (13.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 27.0 mg of colorless liquid in 80% yield. 1 H NMR (400MHz, CDCl3) δ7.57–7.44(m,2H),7.42–7.30(m,3H),7.31–7.25(m,2H),7.19(dd,J=8.0,2. 3Hz, 3H), 5.60–5.40 (m, 1H), 5.11 (dd, J=16.0, 9.5Hz, 1H), 3.25 (d, J=2.7Hz, 1H), 2.81 (dddd, J=13. 0,10.4,5.2,2.3Hz,1H),2.63(dtt,J=10.9,7.1,3.3Hz,1H),2.18–2.03(m,1H),1.78–1.70(m,2H), 1.60(dqd,J=7.7,3.8,2.1Hz,2H),1.49(s,1H),0.94(dd,J=6.9,2.4Hz,3H),0.28(t,J=2.7Hz,6H). 13 C NMR (101MHz, CDCl3) δ142.5,138.5,133.6,130.9,129.1,128.5,128.4,128.4,127 .9,125.7,74.3,43.7,36.2,32.2,22.2,17.1,-3.2,-3.4.HRMS(ESI)calcd.for[C 22 H 30 NaOSi,M+Na] + :361.1958,found:361.1958.

[0186] Example 36

[0187] Synthesis of (E)-1-((tert-butyldimethylsilyl)oxy)-8-(dimethyl(phenyl)silyl)-5-methyloct-6-en-4-ol(4n). The reaction formula and reaction process are as follows:

[0188]

[0189] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1n (20.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 38.1 mg of colorless liquid, with a yield of 94%. 1 H NMR (400MHz, CDCl3) δ7.62–7.55(m,2H),7.47–7.41(m,3H),5.55(dt,J=15.6,7. 9Hz,1H),5.24(dd,J=15.3,8.4Hz,1H),3.72(t,J=5.9Hz,2H),3.37(t,J=6.0Hz,1 H),2.20(q,J=7.0Hz,1H),2.10(s,1H),1.80(d,J=8.0Hz,2H),1.74–1.62(m,3H), 1.44–1.36(m,1H),1.05(d,J=6.8Hz,3H),0.99(s,9H),0.37(s,6H),0.15(s,6H). 13 C NMR (101MHz, CDCl3) δ138.6,133.6,133.6,131.2,129.0,127.8,127.6,74.8,63.4, 43.4,30.8,29.2,26.0,22.0,18.3,17.0,-3.3,-3.4,-5.3.HRMS(ESI)calcd.for[C 23 H 42 NaO2Si2,M+Na] + :429.2616,found:429.2614.

[0190] Example 37

[0191] Synthesis of (E)-9-chloro-1-(dimethyl(phenyl)silyl)-4-methylnon-2-en-5-ol(4o). The reaction formula and reaction process are as follows:

[0192]

[0193] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1o (12.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 28.8 mg of colorless liquid, with a yield of 89%. 1 H NMR (400MHz, CDCl3) δ7.52–7.47(m,2H),7.35(dd,J=4.4,2.1Hz,3H),5.48(dt,J=15.6,8.0Hz,1 H),5.10(dd,J=15.2,8.5Hz,1H),3.52(t,J=6.7Hz,2H),3.22(ddd,J=9.0,6.3,3.0Hz,1H),2.14 –2.01(m,1H),1.81–1.73(m,2H),1.71(d,J=8.0Hz,2H),1.58(ddt,J=10.3,4.0,2.5Hz,1H),1.4 6(tdd,J=10.7,5.6,3.3Hz,3H),1.34–1.27(m,1H),0.94(d,J=6.8Hz,3H),0.28(d,J=2.0Hz,6H). 13 C NMR(101MHz, CDCl3)δ138.4,133.6,130.8,129.1,128.4,127.8,74.7,45.0,43.5,33.4,32.7,23.2,22.1,17.1,-3.3,-3.4.HRMS(ESI)calcd.for[C 18 H 29 ClNaOSi,M+Na] + :347.1568,found:347.1570.

[0194] Example 38

[0195] Synthesis of (E)-9-(dimethyl(phenyl)silyl)-6-methylnon-7-ene-1,5-diol(4p). The reaction formula and reaction process are as follows:

[0196]

[0197] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1p (10.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 21.1 mg of colorless liquid, with a yield of 69%. 1 H NMR (400MHz, CDCl3) δ7.49 (dd, J=6.5, 3.0Hz, 2H), 7.36 (dd, J=4.4, 2.1Hz, 3H), 5.47 (d t,J=15.6,8.0Hz,1H),5.10(dd,J=15.3,8.4Hz,1H),3.63(t,J=6.2Hz,2H),3.24(ddd, J=8.9,6.4,2.8Hz,1H),2.07(dt,J=8.4,6.5Hz,1H),1.78(s,2H),1.71(d,J=7.9Hz,2H ),1.61–1.47(m,4H),1.41–1.29(m,2H),0.94(d,J=6.8Hz,3H),0.28(d,J=2.0Hz,6H). 13 C NMR(101MHz, CDCl3)δ138.5,133.6,130.9,129.1,128.3,127.8,74.8,62.8,43.5,33.7,32.7,22.1,21.8,17.1,-3.3,-3.4.HRMS(ESI)calcd.for[C 18 H 30 NaO2Si,M+Na] + :329.1907,found:329.1906.

[0198] Example 39

[0199] Synthesis of (E)-9-(dimethyl(phenyl)silyl)-6-methyl-1-(trimethylsilyl)non-7-en-1-yn-5-ol(4q). The reaction formula and reaction process are as follows:

[0200]

[0201] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1q (15.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 27.2 mg of colorless liquid, with a yield of 76%. 1 H NMR(400MHz, CDCl3)δ7.49(t,J=3.6Hz,2H),7.38–7.32(m,3H),5.46(dt,J=15.6, 8.0Hz,1H),5.11(dd,J=15.3,8.4Hz,1H),3.38–3.30(m,1H),2.37–2.24(m,2H),2. 09(h,J=6.9Hz,1H),1.71(d,J=8.1Hz,2H),1.68–1.64(m,1H),1.60(d,J=10.9Hz, 1H),1.52–1.43(m,1H),0.96(d,J=6.8Hz,3H),0.28(d,J=2.1Hz,6H),0.15(s,9H). 13 C NMR(101MHz, CDCl3)δ138.3,133.4,130.4,128.9,128.1,127.7,107.3,84.5,73.9,43.1,33.0,22.0,16.8,16.4,-0.0,-3.5,-3.6.HRMS(ESI)calcd.for[C 21 H 34 NaOSi2,M+Na] + :381.2040,found:381.2040.

[0202] Example 40

[0203] Synthesis of (2E,6E)-8-(dimethyl(phenyl)silyl)-3,5-dimethylocta-2,6-dien-4-ol(4r). The reaction formula and reaction process are as follows:

[0204]

[0205] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.1 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1r (8.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 22.5 mg of colorless liquid, with a yield of 78%. 1 H NMR (400MHz, CDCl3) δ7.53–7.46(m,2H),7.39–7.31(m,3H),5.53(dd,J=15.4,7.8Hz,1H),5.42(q,J=7.0Hz,1H),5.08(dd,J=15.2,8.7Hz,1H),3.47( d,J=8.9Hz,1H),2.18(ddt,J=15.6,8.8,6.7Hz,1H),1.75–1.68(m,3H),1. 63–1.58(m,3H),1.56(s,3H),0.78(d,J=6.8Hz,3H),0.28(d,J=3.3Hz,6H). 13 C NMR (101MHz, CDCl3) δ138.4,135.5,133.6,131.9,129.1,128.7,127.8,123.1,81.6,41.7,22.1,17.5,13.1,10.6,-3.3,-3.5.HRMS(ESI)calcd.for[C 18 H 28 NaOSi,M+Na] + :311.1802,found:311.1801.

[0206] Example 41

[0207] Synthesis of (E)-1-([1,1'-biphenyl]-4-yl)-5-(dimethyl(phenyl)silyl)pent-3-en-1-ol(4s). The reaction formula and reaction process are as follows:

[0208]

[0209] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2b (8.1 mg, 0.15 mmol), and 1s (18.2 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 27.1 mg of colorless liquid, with a yield of 73%. 1 H NMR (400MHz, CDCl3) δ7.59–7.56(m,2H),7.54(d,J=8.2Hz,2H),7.50–7.45(m,2 H),7.42(t,J=7.6Hz,2H),7.37–7.31(m,6H),5.54(dt,J=15.6,8.0Hz,1H),5.28 –5.12(m,1H),4.62(dd,J=7.7,5.1Hz,1H),2.47(q,J=7.0,6.2Hz,1H),2.39(dd ,J=14.0,7.6Hz,1H),2.00(s,1H),1.71(d,J=8.0Hz,2H),0.25(d,J=1.2Hz,6H). 13 C NMR (101MHz, CDCl3) δ143.1,141.0,140.3,138.5,133.6,130.7,129.1,128.8,127.9,1 27.2,127.1,127.1,126.3,124.4,73.3,43.0,22.2,-3.3,-3.4.HRMS(ESI)calcd.for[C 25 H 28 NaOSi,M+Na] + :395.1802,found:395.1803.

[0210] Example 42

[0211] Synthesis of (7S,E)-1-(dimethyl(phenyl)silyl)-4,7,11-trimethyldodeca-2,10-dien-5-ol(4t). The reaction formula and reaction process are as follows:

[0212]

[0213] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1t (15.4 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent (1 / 10), yielding 21.1 mg of colorless liquid in 59% yield (containing diastereomer dr = 2:1). 1 H NMR (400MHz, CDCl3) δ7.54–7.45(m,2H),7.43–7.29(m,3H),5.56–5.38(m,1H),5.12(dd,J=15.6,8.3Hz,2H),3.33(d,J=4.5Hz,1H),2.00(dt,J= 16.0,7.4Hz,3H),1.70(d,J=15.7Hz,6H),1.60(s,3H),1.45–1.27(m,3H ),1.16(tdt,J=13.3,10.3,4.3Hz,2H),0.98–0.84(m,6H),0.28(s,6H). 13 C NMR (101MHz, CDCl3) δ138.5,133.6,131.1,130.7,129.1,128.1,127.8,125.0,124.9,73.0,72.5,44.2,43.7,42.2,4 1.8,38.3,36.2,29.4,29.0,25.7,25.6,25.4,22.1,20.5,18.9,17.7,17.2,17.1,-3.3,-3.4.HRMS(ESI)calcd.for[C 23 H 38 NaOSi,M+Na] + :381.2584,found:381.2588.

[0214] Example 43

[0215] The synthesis of (E)-5-(dimethyl(phenyl)silyl)-2-methyl-1-((R)-4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)pent-3-en-1-ol(4u). The reaction formula and reaction process are as follows:

[0216]

[0217] Ni(COD)₂ (1.4 mg, 0.005 mmol), CyJohnPhos (2.1 mg, 0.006 mmol), ethanol (0.2 mL), PhMe₂SiBpin (52.4 mg, 0.2 mmol), starting material 2a (15.0 μL, 0.15 mmol), and 1u (15.0 mg, 0.1 mmol) were added sequentially to a reaction flask. The reaction was carried out at 25 °C under argon atmosphere for 12 hours, then cooled to 0 °C. The reaction was quenched by adding saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was separated by column chromatography with ethyl acetate / petroleum ether as the eluent, yielding 31.8 mg of colorless liquid in 90% yield (containing diastereomer dr = 1:1). 1 H NMR (400MHz, CDCl3) δ7.52–7.47(m,2H),7.38–7.34(m,3H),5.65–5.59(m,1H),5. 53(ddd,J=15.7,7.9,3.6Hz,1H),5.13–5.03(m,1H),4.74–4.68(m,2H),3.49(dd,J =12.0,8.6Hz,1H),2.26–2.06(m,4H),2.04–1.88(m,2H),1.82(s,1H),1.72(d,J= 6.9Hz, 6H), 1.52–1.42 (m, 1H), 0.82 (dd, J=6.8, 3.0Hz, 3H), 0.29 (d, J=2.8Hz, 6H). 13 C NMR (101MHz, CDCl3) δ150.0,149.7,138.4,138.4,137.3,137.2,133.6,133.6,131.9,131.5,129.1,128.9,128.7,127.8,125.4,124.5,108 .6,80.1,79.9,41.7,41.6,41.6,40.9,30.7,30.4,27.6,27.4,23.5,23.3,22.2,20.9,20.7,17.5,-3.3,-3.3,-3.4.HRMS(ESI)calcd.for[C 23 H 34 NaOSi,M+Na] + :377.2271,found:377.2273.

[0218] Example 44

[0219] Synthesis of (E)-7-(dimethyl(phenyl)silyl)-4-methyl-1-phenylhept-5-en-3-ol(4m). The reaction formula and reaction process are as follows:

[0220]

[0221] Ni ( t Bu-stb)3 (140 mg, 0.15 mmol), CyJohn Phos (63 mg, 0.18 mmol), and ethanol (30 mL), PhMe2SiBpin (3144 mg, 12 mmol), starting material 2a (612.5 mg, 9 mmol), 1m (804.4 mg, 6 mmol), reacted at 25 °C under argon atmosphere for 30 hours, then cooled to 0 °C, the reaction was quenched by adding saturated ammonium chloride solution, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography with ethyl acetate / petroleum ether = 1 / 10 as the eluent, yielding 1.80 g of colorless liquid, with a yield of 89%. 1 H NMR (400MHz, CDCl3) δ7.57–7.44(m,2H),7.42–7.30(m,3H),7.31–7.25(m,2H),7.19(dd,J=8.0,2. 3Hz, 3H), 5.60–5.40 (m, 1H), 5.11 (dd, J=16.0, 9.5Hz, 1H), 3.25 (d, J=2.7Hz, 1H), 2.81 (dddd, J=13. 0,10.4,5.2,2.3Hz,1H),2.63(dtt,J=10.9,7.1,3.3Hz,1H),2.18–2.03(m,1H),1.78–1.70(m,2H), 1.60(dqd,J=7.7,3.8,2.1Hz,2H),1.49(s,1H),0.94(dd,J=6.9,2.4Hz,3H),0.28(t,J=2.7Hz,6H). 13 C NMR (101MHz, CDCl3) δ142.5,138.5,133.6,130.9,129.1,128.5,128.4,128.4,127 .9,125.7,74.3,43.7,36.2,32.2,22.2,17.1,-3.2,-3.4.HRMS(ESI)calcd.for[C 22 H 30 NaOSi,M+Na] + :361.1958,found:361.1958.

Claims

1. A method for synthesizing enepentyl alcohol and its derivatives containing silicon and methyl groups, characterized in that, The reaction formula and reaction process are as follows: A nickel catalyst, a phosphine ligand, a solvent, PhMe2Si-Bpin, the compound of formula 2, and the compound of formula 1 were added sequentially to a reaction vessel. The reaction was stirred in a nitrogen or inert gas atmosphere for 12–30 hours, then cooled to 0°C. The reaction was quenched by adding a saturated ammonium chloride solution, and the solvent was removed under reduced pressure. The mixture was then separated by column chromatography to obtain the compound of formula 3, wherein the phosphine ligand is triethylphosphine, tributylphosphine, or trioctylphosphine.

2. The synthesis method according to claim 1, characterized in that: The nickel catalyst is Ni(COD)2 or Ni( t Bu-stb)3; The solvent is tetrahydrofuran, toluene, mesitylene, or n-hexane; The phosphine ligand is triethylphosphine.

3. The synthesis method according to claim 1, characterized in that: The molar ratio of the compound of Formula 1, the nickel catalyst, and the phosphine ligand is 1:(0.05–0.2):(0.06–0.24); The equivalent ratio of the compound of Formula 1, the compound of Formula 2, and PhMe2Si-Bpin is 1:(1.0~2.0):(1.0~3.0); In Equations 1 and 3, R 1 They are all alkyl, aryl, or heteroaryl.

4. The synthesis method according to claim 1, characterized in that: The ratio of the compound in Formula 1 to the solvent is 1 mmol: 1 to 5 mL.

5. The synthesis method according to claim 1, characterized in that: The stirring reaction is carried out at 0–40°C, preferably at 20–30°C; preferably, the stirring reaction time is 12–20 hours.

6. A method for synthesizing 2-methyl-5-silyl-3-enpentanol and its derivatives using nickel catalysis, characterized in that, The reaction formula and reaction process are as follows: A nickel catalyst, a phosphine ligand, a solvent, PhMe2Si-Bpin, the compound of formula 2, and the compound of formula 1 were added sequentially to a reaction vessel. The reaction was stirred for 12–30 hours under a nitrogen or inert gas atmosphere, then cooled to 0°C. The reaction was quenched by adding a saturated ammonium chloride solution, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography to obtain the compound of formula 4. The phosphine ligand is tricyclopentylphosphine, tri-tert-butylphosphine, diphenyl-tert-butylphosphine, dicyclohexylphenylphosphine, dicyclohexyl-tert-butylphosphine, CyJohnPhos, SPhos, XPhos, JohnPhos, RuPhos, or DavePhos.

7. The synthesis method according to claim 6, characterized in that: The nickel catalyst is Ni(COD)2, Ni( t Bu-stb)3 or Ni(COD)(DQ); The solvent is ethanol, methanol, isopropanol, or tert-butanol; The phosphine ligand is CyJohnPhos.

8. The synthesis method according to claim 6, characterized in that: The molar ratio of the compound of Formula 1, the nickel catalyst, and the phosphine ligand is 1:(0.025–0.2):(0.03–0.24); The molar ratio of the compound of Formula 1, the compound of Formula 2, and PhMe2Si-Bpin is 1:(1.0~2.0):(1.0~3.0); In Equations 1 and 4, R 1 It is alkyl, aryl, or heteroaryl; The ratio of the compound in Formula 1 to the solvent is 1 mmol: 1 to 5 mL.

9. The synthesis method according to claim 6, characterized in that: The stirring reaction is carried out at 0–40°C, preferably at 20–30°C; preferably, the stirring reaction time is 12–20 hours.

10. The synthesis method according to claim 1 or 6, characterized in that, The compound of Formula 1 is one of the following compounds:

Images