Iron-catalyzed hydroboration and hydrosilylation of alkynes and applications thereof

Abstract

The application provides an iron catalytic system for acetylene compound boron hydrogenation and silicon hydrogenation reaction, which comprises an acetylene compound, an iron salt catalyst, a boron reagent or a silicon reagent, an alcohol, an alkoxy base and a solvent. The application also provides an application of the iron catalytic system, which is used for catalyzing acetylene compound boron hydrogenation or silicon hydrogenation reaction to synthesize alkenyl borate or alkenyl silane. The method is as follows: taking an iron salt as a catalyst, an alcohol as a hydrogen source, and participating in a base and a solvent, catalyzing the gamma-region selective and cis stereoselective boron hydrogenation or silicon hydrogenation reaction of the acetylene compound and the boron reagent or the silicon reagent to synthesize alkenyl borate or alkenyl silane. The application can realize gamma-region selective and cis stereoselective addition under the iron catalytic system, and has the outstanding advantages of wide substrate range, high region selectivity and stereoselectivity, mild reaction condition, green environmental protection, no harm to human body and suitability for industrial production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to an iron catalysis system for boron hydride and silicon hydride reactions of acetylene compounds and application thereof. BACKGROUND

[0002] Alkenyl boronate as a highly versatile organic synthesis building block has extremely high synthetic application value, and can be used for Suzuki-Miyaura cross-coupling reaction and Chan-Lam coupling reaction to convert C-B bond into C-O bond, C-N bond, C-F bond and C-C bond, so as to construct complex drug molecules; and can be widely applied in the fields of medicine, liquid crystal material, organic functional material and the like.

[0003] Alkenyl silane as a valuable intermediate can also be subjected to extensive chemical conversion, and its application value is embodied in that carbon-carbon bond can be formed through Sakurai allylation, Hiyama cross-coupling and the like.

[0004] Transition metal catalysis of acetylene boron hydride or silicon hydride reaction is the most important method for synthesizing alkenyl boronate or alkenyl silane, however, in the boron hydride or silicon hydride reaction of acetylene, the problem of difficult control of regioselectivity and stereoselectivity inevitably occurs, leading to generation of a mixture containing multiple isomers. In previous studies, the control of regioselectivity and stereoselectivity of acetylene boron hydride or silicon hydride reaction is mainly realized through precious metals such as palladium, rhodium and iridium and addition of additional ligands, and these methods mostly use expensive or toxic metals and ligands, which not only increases the synthesis cost of products, but also generates a large amount of toxic wastewater in the post-processing of reaction, which is contrary to the concept of green chemistry and sustainable development.

[0005] Based on this, the application uses iron which is abundant in earth reserves, cheap and easy to obtain and non-toxic to biology as a catalyst and does not need to add additional ligands, establishes an iron catalysis system for boron hydride and silicon hydride reactions of acetylene compounds which has extremely high application value, and the regioselectivity and stereoselectivity are specific, thereby providing a green and sustainable efficient catalysis system for boron hydride and silicon hydride reactions of acetylene compounds, which has extremely high industrial application value. SUMMARY

[0006] The technical problem to be solved by the application is to provide an iron catalysis system for boron hydride and silicon hydride reactions of acetylene compounds and application thereof in view of the deficiencies of the prior art, which is a green and sustainable efficient tool and can selectively synthesize polysubstituted alkenyl boronate or alkenyl silane, realizes gamma-regioselective and cis-stereoselective addition of acetylene compounds, and has the outstanding advantages of wide substrate range, high selectivity, mild reaction conditions and the like.

[0007] To solve the above technical problems, the technical scheme adopted by the present application is: an iron catalytic system for boron hydride and silicon hydride reactions of acetylene compounds, characterized in that the system comprises acetylene compounds, an iron salt catalyst, a boron reagent or a silicon reagent, an alkoxy base and a solvent;

[0008] The iron catalytic system is in a water-free and oxygen-free environment.

[0009] The molar ratio of the iron salt catalyst to the acetylene compounds is 0.05:1-0.15:1.

[0010] The molar ratio of the alkoxy base to the acetylene compounds is 1:1-2:1.

[0011] The molar ratio of the boron reagent or the silicon reagent to the acetylene compounds is 1:1-2:1.

[0012] Preferably, the iron catalytic system further comprises an alcohol; the molar ratio of the alcohol to the acetylene compounds is 0:1-5:1.

[0013] Preferably, the acetylene compounds comprise internal propargyl alcohol, internal propargyl amine, terminal propargyl alcohol or terminal propargyl amine, and the general formulae are as follows:

[0014]

[0015] Preferably, the boron reagent used in the boron hydride reaction comprises pinacol diboron, pinacol glycol diboron, pinacol neopentyl glycol diboron or (dimethylaminonaphthyl) pinacol boronic acid; the silicon reagent used in the silicon hydride reaction comprises (dimethylphenylsilyl) pinacol boronic acid or (triethylsilyl) pinacol boronic acid.

[0016] Preferably, the alkoxy base is alkoxy lithium, alkoxy sodium or alkoxy potassium.

[0017] The alkoxy group in the alkoxy base comprises methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or tert-pentoxy.

[0018] Preferably, the solvent is a polar solvent, a non-polar solvent or a mixed solvent.

[0019] The polar solvent comprises an alcohol solvent, a halogenated hydrocarbon solvent, a benzene solvent, an ether solvent, a sulfone solvent or an amide solvent.

[0020] The non-polar solvent comprises an alkane solvent.

[0021] The mixed solvent is a solvent obtained by mixing a plurality of solvents in different proportions, such as a mixed solvent of toluene and ethylbenzene, a mixed solvent of methyl tert-butyl ether and ethanol, a mixed solvent of xylene, tetrahydrofuran and dimethyl sulfoxide, etc.

[0022] Preferably, the iron salt catalyst comprises an organic complexed iron salt, an organic acid iron salt, an inorganic acid iron salt, a sulfonic acid iron salt, or a heteropoly acid iron salt;

[0023] The organic complexed iron salt comprises acetylacetone iron, acetylacetone ferrous, or porphyrin iron;

[0024] The organic acid iron salt comprises a divalent iron salt and / or a trivalent iron salt; the organic acid in the organic acid iron salt comprises acetic acid, stearic acid, oleic acid, or citric acid;

[0025] The inorganic acid iron salt comprises a divalent iron salt and / or a trivalent iron salt; the inorganic acid in the inorganic acid iron salt comprises hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrogen sulfide acid, hydrogen cyanide acid, or carbonic acid;

[0026] The sulfonic acid iron salt comprises a divalent iron salt and / or a trivalent iron salt; the sulfonic acid in the sulfonic acid iron salt comprises benzene sulfonic acid, p-toluene sulfonic acid, nitrobenzene sulfonic acid, halogenated benzene sulfonic acid, or trifluoromethane sulfonic acid;

[0027] The heteropoly acid iron salt comprises a divalent iron salt and / or a trivalent iron salt; the heteropoly acid in the heteropoly acid iron salt comprises phosphomolybdic acid or phosphotungstic acid.

[0028] Preferably, the alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or tert-butanol.

[0029] The application also provides an application of the iron catalytic system for the boron hydride and silicon hydride reactions of the alkyne compound, which is used for catalyzing the boron hydride or silicon hydride reactions of the alkyne compound to synthesize alkenyl borate or alkenyl silane with γ-regioselectivity and cis stereoselectivity.

[0030] The application also provides a method for synthesizing alkenyl borate or alkenyl silane by iron catalyzing the boron hydride and silicon hydride reactions of the alkyne compound, which comprises the following steps:

[0031] S1, adding a boron reagent or a silicon reagent, an iron salt catalyst, and an alkoxy base into a reactor;

[0032] S2, tightly plugging the reactor with a vacuum silicone plug, vacuumizing and filling argon for 3 times, and sealing the reactor;

[0033] S3, under the protection of argon, sequentially adding an alkyne compound, an alcohol, and a solvent into the reactor by using a syringe; the molar ratio of the iron salt catalyst to the alkyne compound is 0.05:1-0.5:1; the molar ratio of the alkoxy base to the alkyne compound is 1:1-3:1; the molar ratio of the boron reagent or the silicon reagent to the alkyne compound is 1:1-3:1; and the molar ratio of the alcohol to the alkyne compound is 0:1-5:1.

[0034] S4, stirring the reaction at a temperature of 25-80℃ for 6h;

[0035] S5, after the reaction, quenching the reaction by adding water, then extracting the reaction solution with petroleum ether and ethyl acetate for three times, and taking the organic phase; drying with anhydrous sodium sulfate, then rotary evaporation, and then column chromatography to obtain the alkenyl borate or alkenyl silane;

[0036] In the method, when the boron reagent is used in step S1, the alkyne compound undergoes borohydration reaction to synthesize the alkenyl borate; when the silicon reagent is used in step S1, the alkyne compound undergoes silicohydration reaction to synthesize the alkenyl silane.

[0037] Preferably, the temperature in S4 is 25-80℃ by placing the reactor in an oil bath pot at a predetermined temperature and stirring the reaction.

[0038] Preferably, the volume ratio of petroleum ether to ethyl acetate used in the extraction process in S5 is 1:1-10:1.

[0039] Preferably, the eluent used in the column chromatography in S5 is petroleum ether and ethyl acetate with a volume ratio of 1:1-10:1.

[0040] In the method for synthesizing alkenyl borate or alkenyl silane by iron-catalyzed borohydration or silicohydration of alkyne compounds, the borohydration or silicohydration reaction shows specific γ-regioselectivity and cis-stereoselectivity addition, and the reaction scheme is shown in the following figure:

[0041]

[0042] Compared with the prior art, the present application has the following advantages:

[0043] 1. The iron-catalyzed borohydration and silicohydration reaction system designed in the present application uses iron salt which is abundant in earth reserves, cheap and easy to obtain and non-toxic to biology as catalyst, does not need to add additional ligand, and uses solvent with low boiling point or easy to dissolve in water, which is convenient for post-treatment. As a kind of green and sustainable efficient tool, the catalytic system can selectively synthesize polysubstituted alkenyl borate or alkenyl silane.

[0044] 2. The present application has wide substrate range, high reaction conversion rate, specific regioselectivity and stereoselectivity, and mild reaction conditions, which is suitable for industrial production.

[0045] The present application will be further described in detail below in combination with the drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 is the reaction mechanism diagram of the present application.

[0047] Figure 2 and Figure 3 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 1 of the present application.

[0048] Figure 4 and Figure 5 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 2 of the present application.

[0049] Figure 6 and Figure 7 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 3 of the present application.

[0050] Figure 8 and Figure 9 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 4 of the present application.

[0051] Figure 10 and Figure 11 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 5 of the present application.

[0052] Figure 12 and Figure 13 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 6 of the present application.

[0053] Figure 14 and Figure 15 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 7 of the present application.

[0054] Figure 16 and Figure 17 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 8 of the present application.

[0055] Figure 18 and Figure 19 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 9 of the present application.

[0056] Figure 20 and Figure 21 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 10 of the present application.

[0057] Figure 22 and Figure 23 are respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum of Example 11 of the present application. DETAILED DESCRIPTION

[0058] All reactions of the present application are carried out in argon and degassed solvents.

[0059] Example 1

[0060] The method of the present embodiment for synthesizing alkenyl boronate by iron-catalyzed hydroboration of alkyne compound is carried out by using the chemical reaction formula shown as follows:

[0061]

[0062] Fe(acac)3(tris(acetylacetone)iron, 0.01 mmol), LiO t Bu(lithium tert-butoxide, 0.2 mmol), (Bpin)2(pinacol diborane, 0.14 mmol); vacuumize and replace with argon for three times, then add 4-(cyclohexyl-l-enyl)-2-methyl-3-butyne-2-ol (0.1 mmol) into the reactor under argon protection, vacuumize and replace with argon for three times, then add PrOH (isopropanol, 0.2 mmol), tetrahydrofuran (0.5 mL) into the reactor, stir for 6 h at room temperature (25 °C); then add 5 mL water to quench the reaction, extract with petroleum ether and ethyl acetate (10:1, v:v) for three times, dry the combined organic phase with anhydrous sodium sulfate, and concentrate under reduced pressure in a rotary evaporator to obtain the crude product, which is then purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v:v, product R i = 0.4), and evaporate the chromatography liquid to obtain (Z)-4-cyclohexyl-l-enyl)-2-methyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)-3-buten-2-ol as a colorless oily liquid, with a yield of 82%. f = 0.4), and evaporate the chromatography liquid to obtain (Z)-4-cyclohexyl-l-enyl)-2-methyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)-3-buten-2-ol as a colorless oily liquid, with a yield of 82%.

[0063] Figure 2 and Figure 3 The nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic carbon spectrum of this example are shown in Figures 1 and 2, respectively, and the data are as follows:

[0064] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 6.22 (s, 1H), 5.46 (s, 1H), 2.13 - 2.04 (m, 4H), 1.68 - 1.56 (m, 4H), 1.33 (s, 6H), 1.24 (s, 13H);

[0065] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 150.13, 140.63, 122.73, 83.29, 73.71, 37.61, 31.26, 29.80, 24.67, 22.68, 21.90.

[0066] In this example, the base can be lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, or lithium tert-amyl alcohol in addition to lithium tert-butoxide.

[0067] In this example, the iron salt catalyst can be acetylacetone ferrous or porphyrin iron in addition to tris(acetylacetone)iron.

[0068] Example 2

[0069] The method of the present embodiment for synthesizing alkenyl boronate ester by iron-catalyzed hydroboration of alkyne compound is carried out by using the chemical reaction formula as shown below:

[0070]

[0071] Under argon protection, FeCl2(ferric chloride, 0.015 mmol), LiOMe(lithium methoxide, 0.15 mmol), (Bpin)2(pinacol diborane, 0.16 mmol) were sequentially added into a dry 10 mL reactor; after vacuuming and argon replacement for three times, 4-(4-methoxyphenyl)-2-methyl-3-butyn-2-ol (0.1 mmol), EtOH (ethanol, 0.3 mmol), xylene (0.5 mL) were added into the reactor by using a syringe under argon protection, and stirred at room temperature (25 °C) for 6 h; then 5 mL of water was added to quench the reaction, and 2 mL of petroleum ether and ethyl acetate (5:1 by volume) were added to extract three times, the organic phase was combined, dried over anhydrous sodium sulfate, and concentrated by rotary evaporator under reduced pressure; the obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 5:1, v:v, product Rf=0.5) to obtain a colorless oily liquid, which was (Z)-4-(4-methoxyphenyl)-2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-buten-2-ol, with a yield of 81%. f

[0072] Figure 4 and Figure 5 The present embodiment is respectively the hydrogen spectrum and the carbon spectrum of the nuclear magnetic spectrum, and the data are as follows:

[0073] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 7.07 (d, J = 8.3 Hz, 2H), 6.85 (d, J = 8.2 Hz, 2H), 6.57 (s, 1H), 3.79 (s, 3H), 1.73 (s, 1H), 1.30 (s, 6H), 1.24 (s, 12H);

[0074] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 158.08, 152.45, 131.86, 129.30, 113.56, 83.62, 73.21, 55.08, 31.04, 24.66.

[0075] ​In this embodiment, the iron salt catalyst used, in addition to ferrous chloride, can also be ferrous chloride, ferrous fluoride, ferrous fluoride, ferrous bromide, ferrous bromide, ferrous perchlorate, ferrous perchlorate, ferrous sulfate, ferrous sulfate, ferrous phosphate, ferrous phosphate, ferrous pyrophosphate, ferrous pyrophosphate, ferrous sulfide, ferrous sulfide, ferrous cyanide, ferrous cyanide, ferrous carbonate, or ferric carbonate.

[0076] Example 3

[0077] The method for synthesizing alkenyl borate esters by the iron-catalyzed hydroboration reaction of alkynes in this embodiment is carried out using the following chemical reaction formula:

[0078]

[0079] Under argon protection, Fe[P(MoO2)] was added sequentially to a dry 10 mL reactor. 10 )4](ferric phosphomolybdate, 0.01 mmol), LiO t Bu (lithium tert-butoxide, 0.10 mmol), (Bpin)2 (pinacol diboronate, 0.10 mmol); after evacuation and argon purging, and repeated gas replacement three times, 2-phenyl-3-butyn-2-ol (0.1 mmol) was added under argon protection. t BuOH (tert-butanol, 0.2 mmol) and N,N-dimethylacetamide (0.5 mL) were added to the reactor using a syringe and stirred at room temperature (25 °C) for 6 h. Then, 5 mL of water was added to quench the reaction, followed by extraction three times with 2 mL of petroleum ether and ethyl acetate at a volume ratio of 10:1. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure using a rotary evaporator. The crude product was then subjected to silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 10:1, v:v, product R) f =0.6) Separation yielded a colorless oily liquid, namely 2-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaboryl)-3-buten-2-ol, with a yield of 68%.

[0080] Figure 6 and Figure 7 These are the proton and carbon NMR spectra of this embodiment, respectively, with the data as follows:

[0081] 1H NMR data: 1 H NMR(500MHz,Chloroform-d)δ7.48–7.43(m,2H),7.36–7.30(m,2H),7.27–7.20(m,1H), 6.87(d,J=18.1Hz,1H),5.69(d,J=18.1Hz,1H),2.00(s,1H),1.66(s,3H),1.26(s,12H);

[0082] NMR Carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 158.10, 145.78, 128.22, 126.96, 125.22, 83.32, 75.32, 29.10, 24.79.

[0083] The iron salt catalyst used in this embodiment can be ferrophosphomolybdate, ferrophosphotungstate or iron phosphotungstate in addition to ferrophosphomolybdate.

[0084] Example 4

[0085] The method for synthesizing alkenyl borate by iron catalyzed hydroboration of alkyne compound in this embodiment is carried out by using the chemical reaction formula as shown below:

[0086]

[0087] Under argon protection, Fe(OAc)2(ferric acetate, 0.005 mmol), LiO t Bu (lithium tert-butoxide, 0.15 mmol), (Bpin)2(pinacol diborane, 0.15 mmol) were sequentially added into a dry 10 mL reactor; after vacuum and argon replacement for three times, ethynylestradiol (0.1 mmol), MeOH (methanol, 0.1 mmol), dichloroethane (0.5 mL) were added into the reactor by using a syringe under argon protection, and stirred at room temperature (25°C) for 6 h; then 5 mL water was added to quench the reaction, and 2 mL petroleum ether and ethyl acetate (1:1 by volume) were added to extract three times, and the organic phase was combined, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator under reduced pressure; the obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 1:1, v:v, product R f =0.3) to obtain white solid, which was (8R,9S,13S,14S,17R)-13-methyl-17-(E)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)ethenyl)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthrene-3,17-diol, with a yield of 46%.

[0088] Figure 8 and Figure 9 The nuclear magnetic spectrum hydrogen spectrum and nuclear magnetic carbon spectrum of this embodiment are shown in Figures 1 and 2 respectively, and the data are as follows:

[0089] NMR Hydrogen spectrum data: 1H NMR (500 MHz, Chloroform-d) δ 7.02 - 6.88 (m, 2H), 6.62 - 6.55 (m, 2H), 5.67 (d, J = 18.2 Hz, 1H), 2.90 - 2.58 (m, 2H), 2.09 - 1.78 (m, 5H), 1.68 (s, 1H), 1.60 (s, 1H), 1.48 - 1.35 (m, 2H), 1.34 (s, 12H), 1.27 - 1.17 (m, 7H), 0.86 (s, 3H);

[0090] 1.89 (m, 3H), 1.87 - 1.78 (m, 1H), 1.68 (s, 1H), 1.60 (s, 1H), 1.48 - 1.35 (m, 2H), 1.34 (s, 12H), 1.27 - 1.17 (m, 7H), 0.86 (s, 3H);

[0091] NMR Carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 158.56, 154.02, 138.32, 132.37, 125.92, 115.39, 112.06, 84.93, 83.90, 49.16, 47.11, 42.31, 38.87, 37.02, 32.28, 29.64, 27.13, 25.75, 24.73 (d, J = 31.0 Hz), 23.36, 14.12.

[0092] The iron salt catalyst used in this embodiment can be ferrous acetate, ferric acetate, ferrous stearate, ferric stearate, ferrous oleate, ferrous citrate or ferric citrate in addition to ferrous acetate.

[0093] Example 5

[0094] The method for synthesizing alkenyl boronate by iron-catalyzed hydroboration of alkyne compounds in this embodiment is carried out using the chemical reaction formula shown below:

[0095]

[0096] Under argon protection, Fe(OTf)3(iron triflate, 0.01 mmol), LiO t Bu (lithium tert-butoxide, 0.15 mmol), Bdan-Bpin ((dimethylaminonaphthalenyl)boronic acid-pinacol ester, 0.17 mmol) were sequentially added into a dry 10 mL reactor; after vacuum and argon replacement for three times, 2-methyl-3-octyn-2-ol (0.1 mmol), ethanol (0.5 mL) were added into the reactor by syringe under argon protection, and stirred at 40°C for 6 h; then 5 mL water was added to quench the reaction, and 2 mL petroleum ether and ethyl acetate (7.5:1 by volume ratio) were added to extract three times, the organic phase was combined, dried over anhydrous sodium sulfate, and concentrated by rotary evaporator under reduced pressure; the obtained crude product was subjected to silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 7.5:1, v:v, product Rf = 0.3) to give a blue-purple solid, which was 2-methyl-4- (dimethylaminonaphthyl) -3-octen-2-ol, yield 80%.

[0097] Figure 10 and Figure 11 The nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the present example are shown in Figures 1 and 2, respectively, and the data are as follows:

[0098] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, DMSO-d6) δ 7.66 (s, 2H), 7.06 (t, J = 7.8 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 6.56 (d, J = 7.6 Hz, 2H), 6.12 (s, 1H), 3.48 (s, 1H), 2.59 (t, J = 7.3 Hz, 2H), 1.45 - 1.26 (m, 10H), 0.92 (t, J = 6.8 Hz, 3H);

[0099] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, DMSO-d6) δ 146.41, 143.02, 136.35, 128.02, 119.89, 116.22, 105.80, 71.17, 33.30, 31.89, 28.32, 23.13, 14.66.

[0100] The iron salt catalyst used in the present example can be ferrous benzene sulfonate, ferric benzene sulfonate, ferrous p-toluenesulfonate, ferric p-toluenesulfonate, ferrous nitrobenzene sulfonate, ferric nitrobenzene sulfonate, or ferrous chlorobenzene sulfonate, in addition to ferric triflate.

[0101] Example 6

[0102] The method of the present example for synthesizing alkenyl borate by iron-catalyzed hydroboration of alkyne compound is carried out according to the chemical reaction formula shown below:

[0103]

[0104] In a dry 50 mL reactor, Fe(OTs)2(p-toluenesulfonic acid iron, 0.05 mmol), KOMe (potassium methoxide, 1.5 mmol), (Bpin)2(pinacol diborane, 1.3 mmol) were added successively under argon protection; vacuum and argon were replaced for three times successively, then 4-((2-methylbut-3-yn-2-ylamino)methyl)benzonitrile (1 mmol), methyl tert-butyl ether (5 mL) were added into the reactor by syringe under argon protection, stirred at 40 °C for 6 h; then 25 mL water was added to quench the reaction, 20 mL petroleum ether and ethyl acetate (7.5:1, v:v) were added to extract three times, the organic phase was combined, dried over anhydrous sodium sulfate, concentrated by rotary evaporator under reduced pressure, the obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 7.5:1, v:v, product R f = 0.4) to obtain (E)-4-((2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-en-2-yl)amino)benzonitrile as a colorless oily liquid, yield 88%.

[0105] Figure 12 and Figure 13 The nuclear magnetic resonance hydrogen spectrum and nuclear magnetic carbon spectrum of this example are shown in Figures 1 and 2, respectively, and the data are as follows:

[0106] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 7.57 (d, J = 8.2 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 6.54 (d, J = 18.4 Hz, 1H), 5.50 (d, J = 18.4 Hz, 1H), 3.68 (s, 2H), 1.28 (s, 12H), 1.21 (s, 6H);

[0107] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 159.76, 132.04, 128.64, 119.06, 110.37, 83.26, 55.73, 47.08, 29.67, 26.88, 24.78.

[0108] In addition to potassium methoxide, the base used in this example can also be potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium tert-butoxide or potassium tert-amyl alcohol.

[0109] Example 7

[0110] The method for synthesizing alkenyl borate by iron-catalyzed hydroboration of alkyne compound in this example is carried out by using the chemical reaction formula as shown below:

[0111]

[0112] Under argon protection, Fe(OTs)3(ferric p-toluenesulfonate, 0.01 mmol), LiOBu (lithium tert-butoxide, 0.15 mmol), (Bpin)2(pinacol diborane, 0.20 mmol) were sequentially added into a dry 10 mL reactor, which was vacuumed and filled with argon for three times. After that, N-benzyl-4-methyl-dodec-5-yn-4-amine (0.1 mmol) was added into the reactor under argon protection, and the mixture was stirred at room temperature (25 °C) for 6 h. Then, 5 mL water was added to quench the reaction, and the mixture was extracted with 2 mL petroleum ether and ethyl acetate (10:1, v:v) for three times. The combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure on a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v:v, product Rf= 0.4) to obtain (Z)-N-benzyl-4-methyl-6-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)dodec-5- en-4-amine as a colorless oily liquid with a yield of 80%. t Bu(tert-butoxyl lithium, 0.15 mmol), (Bpin)2(pinacol diborane, 0.20 mmol); vacuumed and filled with argon for three times, and then N-benzyl-4-methyl-dodec-5-yn-4-amine (0.1 mmol) was added into the reactor under argon protection. The mixture was stirred at room temperature (25 °C) for 6 h. Then, 5 mL water was added to quench the reaction, and the mixture was extracted with 2 mL petroleum ether and ethyl acetate (10:1, v:v) for three times. The combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure on a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v:v, product Rf= 0.4) to obtain (Z)-N-benzyl-4-methyl-6-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)dodec-5- en-4-amine as a colorless oily liquid with a yield of 80%. n BuOH (n-butanol, 0.3 mmol), N-methylpyrrolidone (0.5 mL) were added into the reactor by syringe, and the mixture was stirred at room temperature (25 °C) for 6 h. Then, 5 mL water was added to quench the reaction, and the mixture was extracted with 2 mL petroleum ether and ethyl acetate (10:1, v:v) for three times. The combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure on a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v:v, product Rf= 0.4) to obtain (Z)-N-benzyl-4-methyl-6-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)dodec-5- en-4-amine as a colorless oily liquid with a yield of 80%. f BuOH (n-butanol, 0.3 mmol), N-methylpyrrolidone (0.5 mL) were added into the reactor by syringe, and the mixture was stirred at room temperature (25 °C) for 6 h. Then, 5 mL water was added to quench the reaction, and the mixture was extracted with 2 mL petroleum ether and ethyl acetate (10:1, v:v) for three times. The combined organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure on a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 10:1, v:v, product Rf= 0.4) to obtain (Z)-N-benzyl-4-methyl-6-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-yl)dodec-5- en-4-amine as a colorless oily liquid with a yield of 80%.

[0113] Figure 14 and Figure 15 The nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic carbon spectrum of this example are shown in Figures 1 and 2, respectively, and the data are as follows:

[0114] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 7.42 - 6.89 (m, 5H), 5.99 (s, 1H), 3.57 (s, 2H), 2.43 - 2.20 (m, 2H), 1.36 - 1.04 (m, 27H), 0.98 - 0.64 (m, 6H);

[0115] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 149.29, 141.55, 128.21, 126.59, 83.03, 58.57, 47.20, 44.01, 31.86, 30.31, 29.81, 29.46, 26.12, 24.72, 24.67, 22.61, 17.20, 14.69, 14.09.

[0116] Example 8

[0117] The method for synthesizing alkenyl borate by iron-catalyzed hydroboration of alkyne compound in this example is carried out according to the chemical reaction formula as shown below:

[0118]

[0119] Under argon protection, Fe(OTf)3 (ferric trifluoromethanesulfonate, 0.01 mmol) was added sequentially to a dry 10 mL reactor. t Bu (potassium tert-butoxide, 0.15 mmol), (Bpai)2 (pinenediol diboronate, 0.17 mmol); After evacuating and purging with argon gas three times, 0.5 mL of a mixture of 2-methyl-3-octyne-2-ol (0.1 mmol), tetrahydrofuran, and dimethyl sulfoxide in any proportion was added to the reactor under argon protection using a syringe. The mixture was stirred at 40 °C for 6 h. Then, 5 mL of water was added to quench the reaction, followed by three extractions with 2 mL of petroleum ether and ethyl acetate (volume ratio 5:1). The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure using a rotary evaporator. The crude product was then subjected to silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 5:1, v:v, product R). f =0.5) to separate a blue-purple solid, namely 2-methyl-4-(3aR,4R,7S,7aS)-3a,8,8-trimethylhexahydro-4,7-toluidine[d][1,3,2]dioxaborane)-3-octen-2-ol, with a yield of 85%.

[0120] Figure 16 and Figure 17 These are the proton and carbon NMR spectra of this embodiment, respectively, with the data as follows:

[0121] 1H NMR data: 1 H NMR(500MHz,Chloroform-d)δ6.30(s,1H),4.28(dd,J=8.8,1.9Hz,1H),2.48–1.81(m,8H),1.72(s ,1H),1.41–1.32(m,12H),1.27(s,3H),1.13(d,J=10.8Hz,1H),0.88(t,J=6.9Hz,3H),0.83(s,3H);

[0122] Carbon NMR data: 13 C NMR(126MHz,Chloroform-d)δ149.87,85.67,77.84,72.42,51.34,39.49,38.11 ,35.61,33.00,30.96,29.68,29.03,28.65,27.08,26.50,24.01,23.09,14.13.

[0123] The mixed solvent used in this embodiment can be a mixture of toluene and ethylbenzene, a mixture of methyl tert-butyl ether and ethanol, a mixture of dimethylbenzene, tetrahydrofuran and dimethyl sulfoxide, etc. in addition to any proportion of tetrahydrofuran and dimethyl sulfoxide.

[0124] Example 9

[0125] The method for synthesizing alkenyl silane by iron-catalyzed hydrosilylation of alkyne compounds in this embodiment is carried out by using the chemical reaction formula as shown below:

[0126]

[0127] Under argon protection, Fe(OTs)3(ferric p-toluenesulfonate, 0.01 mmol), NaO t BuOH (n-butanol, 0.2 mmol), 1,4-dioxane (0.5 mL) were added into the reactor by syringe, and stirred at 80°C for 6 h. Then 5 mL of water was added to quench the reaction, and 2 mL of petroleum ether and ethyl acetate (7.5:1 by volume ratio) were added to extract three times, and the organic phase was combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure by a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 7.5:1, v:v, product R n BuOH (n-butanol, 0.2 mmol), 1,4-dioxane (0.5 mL) were added into the reactor by syringe, and stirred at 80°C for 6 h. Then 5 mL of water was added to quench the reaction, and 2 mL of petroleum ether and ethyl acetate (7.5:1 by volume ratio) were added to extract three times, and the organic phase was combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure by a rotary evaporator. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 7.5:1, v:v, product R f = 0.5) to obtain a colorless oily liquid, which was (E)-1-(2-(dimethylphenyl)silyl)prop-1-en-1-yl)cyclohexan-1-ol with a yield of 88%.

[0128] Figure 18 and Figure 19 The nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic carbon spectrum of this embodiment are shown in Figures 1 and 2, respectively, and the data are as follows:

[0129] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 7.54 - 7.46 (m, 2H), 7.35 (dd, J = 5.0, 1.9 Hz, 3H), 5.86 (q, J = 1.8 Hz, 1H), 1.96 (d, J = 1.8 Hz, 3H), 1.74 - 1.60 (m, 6H), 1.53 - 1.31 (m, 5H), 0.34 (s, 6H);

[0130] Nuclear magnetic carbon spectrum data: 13C NMR (126MHz, Chloroform-d) δ146.14,138.34,137.28,133.93,128.86,127.69,73.41,38.75,25.46,22.48,15.82,-3.39.

[0131] In this embodiment, the alkali used, in addition to sodium tert-butoxide, can also be sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, or sodium tert-amyloxide.

[0132] Example 10

[0133] The method for synthesizing alkenylsilanes by the iron-catalyzed hydrosilylation reaction of alkynes in this embodiment is carried out using the following chemical reaction formula:

[0134]

[0135] Under argon protection, Fe(acac)3 (ferric triacetylacetone, 0.01 mmol) and LiO were added sequentially to a dry 10 mL reactor. t Bu (lithium tert-butoxide, 0.15 mmol), Me2PhSi-Bpin ((dimethylbenzyl)borate pinacol ester, 0.20 mmol); after evacuation and argon purging, and three consecutive gas replacements, N-benzyl-1-(octyl-1-ynyl)cyclohexane-1-amine (0.1 mmol) was added under argon protection. n PrOH (n-propanol, 0.5 mmol) and xylene (0.5 mL) were added to the reactor using a syringe and stirred at 80 °C for 6 h. Then, 5 mL of water was added to quench the reaction, followed by extraction three times with 2 mL of petroleum ether and ethyl acetate at a volume ratio of 10:1. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure using a rotary evaporator. The crude product was then subjected to silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 10:1, v:v, product R). f =0.4) Separation yielded a colorless oily liquid, namely (E)-N-benzyl-1-(2-(dimethylphenyl)silyloct-1-en-1-yl)cyclohexane-1-amine, with a yield of 84%.

[0136] Figure 20 and Figure 21 These are the proton and carbon NMR spectra of this embodiment, respectively, with the data as follows:

[0137] 1H NMR data: 1H NMR(500MHz,Chloroform-d)δ7.63–7.52(m,2H),7.41–7.20(m,8H),5.70(s,1H),3.68(s,2H),2.82–2.40(m,2H) ,1.90–1.78(m,2H),1.69–1.55(m,4H),1.51–1.39(m,4H),1.31–1.11(m,8H),0.85(t,J=7.1Hz,3H),0.42(s,6H);

[0138] Carbon NMR data: 13 C NMR(126MHz,Chloroform-d)δ146.09,142.99,141.77,139.61,133.89,128.65,128.29,128.23 ,127.59,126.60,58.09,46.91,37.92,31.56,30.79,30.02,29.97,25.96,22.57,14.03,-1.79.

[0139] Example 11

[0140] The method for synthesizing alkenylsilanes by the iron-catalyzed hydrosilylation reaction of alkynes in this embodiment is carried out using the following chemical reaction formula:

[0141]

[0142] Under argon protection, FeSO4 (ferrous sulfate, 0.01 mmol), NaOMe (sodium methoxide, 0.15 mmol), and Me2PhSi-Bpin ((dimethylbenzyl)borate pinacol ester, 0.15 mmol) were added sequentially to a dry 10 mL reactor. After evacuation and argon purging, and repeated gas replacement three times, acetylenecyclohexanol (0.1 mmol) was added under argon protection. n A mixture of PrOH (n-propanol, 0.4 mmol), xylene, and N-methylpyrrolidone in any proportion (0.5 mL) was added to the reactor using a syringe and stirred at 80 °C for 6 h. The reaction was then quenched with 5 mL of water, followed by extraction three times with 2 mL of petroleum ether and ethyl acetate in a 10:1 volume ratio. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure using a rotary evaporator. The crude product was then subjected to silica gel column chromatography (eluent: petroleum ether:ethyl acetate = 10:1, v:v, product R). f =0.4) Separation yielded a colorless oily liquid, namely (E)-1-(2-(dimethyl(phenyl)silyl)vinyl)cyclohexane-1-ol, with a yield of 95%.

[0143] Figure 22 andFigure 23 The following are the nuclear magnetic spectrum hydrogen spectrum and the nuclear magnetic carbon spectrum of the present embodiment, respectively, and the data is as follows:

[0144] Nuclear magnetic hydrogen spectrum data: 1 H NMR (500 MHz, Chloroform-d) δ 7.52 (dd, J = 6.5, 3.0 Hz, 2H), 7.36 (dd, J = 4.5, 2.0 Hz, 3H), 6.22 (d, J = 18.9 Hz, 1H), 6.01 (d, J = 18.9 Hz, 1H), 1.71 - 1.61 (m, 2H), 1.59 - 1.49 (m, 7H), 1.41 (s, 1H), 1.33 - 1.24 (m, 1H), 0.35 (s, 6H);

[0145] Nuclear magnetic carbon spectrum data: 13 C NMR (126 MHz, Chloroform-d) δ 155.23, 138.79, 133.79, 128.90, 127.72, 123.07, 72.66, 37.37, 25.49, 21.97, -2.50.

[0146] The above is only a preferred embodiment of the present application, and does not limit the present application in any way. Any simple modification, change, and equivalent change made according to the technical essence of the present application to the above embodiment are still within the protection scope of the present technical solution.

Claims

1. A method for synthesizing alkenyl boronate or alkenyl silane by iron-catalyzed hydroboration or hydrosilation of alkyne compound, characterized in that, The reaction system for synthesizing alkenyl borate or alkenyl silane by iron-catalyzed hydroboration or hydrosilylation of alkyne compounds comprises alkyne compounds, iron salt catalyst, boron reagent or silicon reagent, alkoxy base and solvent, and the system is in anhydrous and anaerobic environment; The alkyne compounds are internal propargyl alcohol, internal propargyl amine, terminal propargyl alcohol or terminal propargyl amine; The iron salt catalyst is acetylacetone iron or acetylacetone ferrous, divalent and / or trivalent iron salt of acetic acid, stearic acid, oleic acid or citric acid, divalent and / or trivalent iron salt of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrogen sulfide acid, hydrogen cyanic acid or carbonic acid, divalent and / or trivalent iron salt of benzene sulfonic acid, p-toluene sulfonic acid, nitrobenzene sulfonic acid, halogenated benzene sulfonic acid or trifluoromethane sulfonic acid, divalent and / or trivalent iron salt of phosphomolybdic acid or phosphotungstic acid; The molar ratio of the iron salt catalyst to the alkyne compounds is 0.05:1-0.15:1; The molar ratio of the alkoxy base to the alkyne compounds is 1:1-2:1; The molar ratio of the boron reagent or silicon reagent to the alkyne compounds is 1:1-2:1; The reaction system for synthesizing alkenyl borate or alkenyl silane by iron-catalyzed hydroboration or hydrosilylation of alkyne compounds optionally comprises ROH, the ROH is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol, and the molar ratio of the ROH to the alkyne compounds is 0:1-5:1; The iron-catalyzed hydroboration or hydrosilylation of alkyne compounds to synthesize alkenyl borate or alkenyl silane exhibits specific γ-regioselectivity and cis stereoselectivity addition, and the reaction general formula is as follows: 。 2. The method of claim 1, wherein, The alkoxy base is alkoxy lithium, alkoxy sodium or alkoxy potassium; the alkoxy group in the alkoxy base is methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or tert-amyl.

3. The method of claim 1, wherein, The solvent is a polar solvent, a non-polar solvent or a mixed solvent; The polar solvent is an alcohol solvent, a halogenated hydrocarbon solvent, a benzene solvent, an ether solvent, a sulfone solvent or an amide solvent; The non-polar solvent is an alkane solvent; The mixed solvent is a solvent obtained by mixing multiple solvents in different proportions, a mixed solvent of toluene and ethylbenzene, a mixed solvent of methyl tert-butyl ether and ethanol, a mixed solvent of dimethylbenzene, tetrahydrofuran and dimethyl sulfoxide.

4. The method of claim 1, wherein, The method for synthesizing alkenyl borate or alkenyl silane by iron-catalyzed hydroboration or hydrosilylation of alkyne compounds comprises the following steps: S1, adding boron reagent or silicon reagent, iron salt catalyst and alkoxy base into a reactor; S2, tightly plugging the reactor with vacuum silicone, repeating vacuuming and argon filling for 3 times, and sealing the reactor; S3, under argon protection, sequentially adding alkyne compounds, solvent and optional ROH into the reactor by using a syringe; the molar ratio of the iron salt catalyst to the alkyne compounds is 0.05:1-0.15:1; the molar ratio of the alkoxy base to the alkyne compounds is 1:1-2:1; the molar ratio of the boron reagent or silicon reagent to the alkyne compounds is 1:1-2:1; and the molar ratio of the ROH to the alkyne compounds is 0:1-5:

1. S4, stirring the reaction at a temperature of 25-80 DEG C for 6h; S5, after the reaction, first add water to quench the reaction, then add petroleum ether and ethyl acetate to extract the reaction liquid three times, and then take the organic phase; dry with anhydrous sodium sulfate, spin dry, then column chromatography to obtain alkenyl borate or alkenyl silane; In the method, when a boron reagent is used in step S1, the alkyne compound undergoes a borohydride reaction to synthesize alkenyl borate; when a silicon reagent is used in step S1, the alkyne compound undergoes a silicon hydrogenation reaction to synthesize alkenyl silane; The volume ratio of petroleum ether and ethyl acetate used in the extraction process is 1:1-10:1; The eluent of the column chromatography is petroleum ether: ethyl acetate = 1:1-10:1.

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