Regional and stereoselective internal olefin synthesis method

Abstract

The invention relates to a method for regioselectively and stereoselectively synthesizing internal olefin, in particular to an olefin isomerization method which is simple and convenient to operate and comprises the following steps: under the condition that a catalyst A is K < + > [O = X (R) R '], olefin generates Z-configuration 2-olefin, intracyclic olefin or intracyclic bridged cycloolefin in a high stereoselectivity manner under the condition of an activating reagent; 1-olefin such as allyl arene and butyl-1-alkenyl arene is used as a raw material for isomerization, and the E-configuration aryl alkene compound is generated with high stereoselectivity; an E / Z-configuration aryl ethylene mixture and Z-configuration aryl ethylene olefin are used as raw materials for isomerization, and the E-configuration aryl olefin compound is generated with high regioselectivity. The method has the characteristics of high efficiency, mild reaction conditions, high purity of product isomers, easiness in separation and the like, is an environment-friendly and efficient internal olefin production scheme, and has very high industrial application prospects.

Description

Technical Field

[0001] This invention relates to a method for synthesizing internal olefins, and more specifically to a method for regio- and stereoselective synthesis of internal olefins. Background Technology

[0002] High-purity regioisomers, positional isomers, and stereoisomers of alkenes are key structural units in many natural products and drug molecules. Furthermore, high-purity internal alkenes provide a prerequisite for achieving highly stereoselective C=C bond transformation and functionalization in related chemical transformations, and are widely used in organic synthesis, drug synthesis, and polymer materials chemistry. Therefore, the application value of efficient and high-purity internal alkene synthesis methods is increasing day by day.

[0003] For a long time, people have been committed to developing synthetic methods for alkenes with high isomer purity. To date, some classic methods for synthesizing internal alkenes have been developed, including the Wittig reaction, transition metal-catalyzed coupling reactions, olefin metathesis reactions, Lindlar-catalyzed hydrogenation of alkynes, and transition metal-catalyzed olefin isomerization reactions. Chem. Rev. 2015, 115 (References 5462-5569; CN201911204170.0), catalyzed isomerization of olefins by heterogeneous Lewis acidic systems (CN201910738800.6), etc., are shown below:

[0004] However, these methods generally suffer from poor selectivity, difficulty in separating the E / Z-configuration mixture in the products, the need for expensive precious metal catalysts and organic ligands, the generation of large amounts of waste due to toxic reagents and harsh reaction conditions, low atom economy, and environmental unfriendliness. Alkali-catalyzed reactions have poor selectivity, and heterogeneous catalysis suffers from problems such as complex industrial preparation of catalysts and instability. Summary of the Invention

[0005] Based on the shortcomings of the above-mentioned olefin isomerization methods, this patent provides a highly efficient, widely applicable, and cost-effective method for synthesizing internal olefins with high regio- and stereoselectivity, as well as a simple olefin isomerization method.

[0006] To achieve the above objectives, this invention provides a method for the stereoselective synthesis of inner olefins using a highly efficient and selective K+[O=X(R)R'] catalyst A in the olefin region, characterized in that the method comprises the following reaction formula:

[0007] The structure K is shown in A. +The [O=X(R)R'] catalyst reacts in an organic solvent at -50~120 °C, using 1-olefins as starting materials for regio- and stereoselective isomerization, as shown in equation (1). Under activating reagent conditions, it generates Z-configured 2-olefins, intracyclic olefins, or intracyclic bridged olefins; using 1-olefins as starting materials for regio- and stereoselective isomerization, as shown in equation (2), it generates E-configured aryl ethylenes; using a mixture of E / Z-configured aryl olefins for selective isomerization, as shown in equation (3), it generates... E - Arylene compounds with a specific configuration.

[0008] Where K + [O=X(R)R ’ The structure of catalyst A is as follows:

[0009] In catalyst A, X is selected from either C or S atoms. When X = C atoms, the structure of catalyst A is as follows:

[0010] Where R, R ’ It is selected from any one or more of alkyl groups such as methyl, ethyl, and propyl, and aryl groups such as phenyl and naphthyl.

[0011] When X = S atoms, the structure of catalyst A is as follows:

[0012] R is selected from any one or more of alkyl groups such as methyl, ethyl, and propyl, and aryl groups such as phenyl and naphthyl.

[0013] The K + The source is selected from KOH, KO t One or more combinations of Bu (potassium tert-butoxide), KNH2 or KN(SiMe3)2; Wherein, the preparation method or synthesis process of A, and K + Source and or Catalyst A is synthesized by dissolving a certain amount of a substance in an organic solvent such as tetrahydrofuran, toluene, diethyl ether, acetonitrile, dimethyl sulfoxide, or N,N-dimethyl sulfoxide in a molar ratio of 1:1 to 1:50 and stirring for 0.5 hours. Catalyst A prepared by this method is then transferred to the desired reaction system.

[0014] The activating agent is selected from any one or more of 18-crown-6 ether, benzo-18-crown-6-ether, or dibenzo-18-crown-6; the organic solvent is selected from one or a combination of two or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, or diethyl ether. In the presence of an activator, this invention uses 1-olefins as starting materials for regio- and stereoselective synthesis. Z 2-olefins with a -configuration, wherein the product olefin In the middle, R 1 R 2 R 3 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc., C1-C 20 Alkyl, heteroatom substituted C1-C 20 Alkyl, C1-C 20 Aryl alkyl groups, heteroatom-substituted C1-C 20 Aryl alkyl, C1-C 20 Alkyl heterocyclic aryl group; heteroatoms are selected from N, O or S, and heterocyclic aryl groups are selected from heteroaryl groups such as pyridyl, quinolinyl, piperazine, furanyl, thiophene or imidazolyl.

[0015] In the presence of an activator, this invention selectively synthesizes intracyclic olefins. In the middle, R 1 R 2 , R 3 , R 4 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc., C1-C 20 Alkyl, C1-C 20 Aryl alkyl; m and n are each independently selected from 0 to 4.

[0016] In the presence of an activator, this invention selectively synthesizes intracyclic bridged olefins. In the middle, R 1 R 2 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc., C1-C 20 Alkyl, C1-C 20 The alkyl group is an aralkyl group, and m and n are each independently selected from 0 to 4.

[0017] In the absence of an activator within the system, this invention utilizes terminal olefins as raw materials to achieve regio and stereoselective synthesis. E - Arylene compounds with this configuration In the middle, R 1 Selected from aryl or substituted aryl groups such as phenyl, naphthyl, pyridyl, quinolinyl, piperazine, furanyl, thiophene, or imidazole; R 2 R 3 Each is independently selected from hydrogen atoms, methyl groups, ethyl groups, etc. (C1-C) 20 Alkyl, C1-C 20 Alkyl groups, aralkyl groups, or various substituted aryl groups; R 4 Selected from methyl, ethyl, propyl or isopropyl.

[0018] This invention is based on E / N - Using mixtures of configurations or arylethylenes as raw materials, regio and stereoselective synthesis E - Arylene compounds with this configuration In the middle, R 1 Selected from aryl groups such as phenyl, naphthyl, pyridyl, quinolinyl, piperazine, furanyl, thiophene, or imidazole; R 2 R 3 R 4 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc., C1-C 20 Alkyl, C1-C 20 Aryl alkyl groups.

[0019] The reaction time for selectively synthesizing Z-configured 2-olefins, intracyclic olefins, and intracyclic bridged cyclic olefins in this invention is 1-24 h.

[0020] The reaction time for selectively synthesizing E-configured arylethylene compounds according to this invention is 0.25-12 h.

[0021] This invention relates to regional and stereoselective synthesis. Z - Methods for 2-olefins with different configurations, intracyclic olefins, and intracyclic bridged olefins, olefins, K + Source, O=X(R)R ’ The molar ratio of the activating reagent is 1:0.05-5:0.05-50:0.06-6.

[0022] This invention relates to regional and stereoselective synthesis. E Methods for -configuration of arylethylene compounds, alkenes, K + The molar ratio of source and O=X(R)R' is 1:0.05-5:0.05-50.

[0023] The beneficial effects of this invention are: This method is characterized by high efficiency, mild reaction conditions, high purity of product isomers, and ease of separation. It is an environmentally friendly and efficient production scheme for internal olefins and has a very high prospect for industrial application. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, those skilled in the art... All other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0025] Example 1 A region- and stereoselective synthesis ZA method for 2-olefins with a -configuration, the specific method is as follows:

[0026] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), N,N-diethylformamide (2 mmol), and tetrahydrofuran (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 hours. Then, terminal olefin 1a (1 mmol) and 18-crown-6 ether (0.3 mmol) were added, and the reaction was stirred at 60 °C for 24 hours. The mixture was then purified by column chromatography to obtain the desired product. Z -Compound 1b, colorless liquid, yield 95%. E:Z = 3:97.

[0027] The 1H NMR spectrum data of compound 1b are as follows: 1H NMR (400 MHz, CDCl3) δ 7.29-7.24, (m, 2H), 7.19-7.15 (m, 3H), 5.62– 5.38 (m, 2H), 2.62 (t, J = 7.8 Hz, 2H), 2.08 (q, J = 7.0 Hz, 2H), 1.72-1.54 (m,5H). Example 2

[0028] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), N,N-diethylformamide (2 mmol), and toluene (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 hours. Then, dicyclohexyl-18-crown-6 ether (0.3 mmol) and terminal olefin 2a (1 mmol) were added, and the reaction was stirred at 80 °C for 24 h. The mixture was then purified by column chromatography to obtain the desired product. Z -Compound 2b, colorless liquid, yield 95%. E:Z = 4:96.

[0029] The 1H NMR spectrum data of compound 2b are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.16-7.01 (m, 1H), 6.70-6.62 (m, 3H), 5.38-5.26 (m, 2H), 3.71 (s, 3H), 2.50 (t, J = 7.6 Hz, 2H), 1.97-1.91 (m, 2H, cis),1.89-1.85 (m, 2H, trans), 1.57-1.49 1.50 (m, 5H), 1.29-1.23 (m, 5H).

[0030] Example 3

[0031] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), N-ethyl-N-phenylformamide (0.5 mmol), and tetrahydrofuran (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of 18-crown-6 ether (0.3 mmol) and terminal olefin 3a (1 mmol). The reaction was carried out at 25 °C for 24 hours, and then purified by column chromatography to obtain the desired product. Z -Compound 3b, colorless liquid, yield 92%. E:Z = 3:97.

[0032] The 1H NMR spectrum data of compound 3b are as follows: H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 2.0 Hz, 1H), 6.28 (dd, J = 3.0, 1.8Hz, 1H), 5.98 (dd, J = 3.0, 1.0 Hz, 1H), 5.52 – 5.36 (m, 2H), 2.63 (t, J = 7.6Hz, 2H), 2.09 (q, J = 7.4 Hz, 2H), 1.74 – 1.57 (m, 5H). Example 4

[0033] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), N,N-dimethylformamide (0.5 mL), and N,N-dimethylacetamide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours. Then, benzo[1]18-crown-6 ether (0.3 mmol) and terminal olefin 4a (1 mmol) were added. The reaction was then stirred at 25 °C for 24 h. Column chromatography was used to separate the Z-configuration compound 4b as a colorless liquid in 92% yield. E:Z = 2:98.

[0034] The 1H NMR spectrum data of compound 4b are as follows: 1H NMR (400 MHz, CDCl3) δ 5.38 – 5.28 (m, 2H), 1.95 (q, J = 6.7 Hz, 2H), 1.53 (d, J = 6.0 Hz, 3H), 1.29 – 1.19 (m, 14H), 0.81 (t, J = 6.8 Hz, 3H).

[0035] Example 5

[0036] Under a nitrogen atmosphere at room temperature, KNH2 (0.5 mmol), N,N-diethylformamide (2 mmol), and toluene (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 hours. Then, terminal olefin 5a (1 mmol) and 18-crown-6 ether (0.6 mmol) were added, and the reaction was stirred at 0 °C for 24 h. The mixture was then purified by column chromatography to obtain the desired product. Z -Compound 5b, colorless liquid, yield 92%. E:Z = 8:92.

[0037] The 1H NMR spectrum data of compound 5b are as follows: 1H NMR (400 MHz, CDCl3) δ 6.81 (s, 4H), 5.44 – 5.32 (m, 4H), 3.93 (t, J = 6.4 Hz, 4H), 2.18 (q, J = 7.2 Hz, 4H), 1.84 – 1.77 (m, 1H), 1.54 (d, J = 6.4Hz, 6H).

[0038] Example 6

[0039] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), dimethyl sulfoxide (2 mmol), and N,N-dimethylacetamide (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 h. Then, terminal olefin 6a (1 mmol) and benzo[18-crown-6] ether (0.3 mmol) were added, and the reaction was stirred at 25 °C for 12 h. The Z-configuration compound 6b was purified by column chromatography as a colorless liquid with a yield of 95%. E:Z = 5:95.

[0040] The 1H NMR spectrum data of compound 6b are as follows: 1H NMR (400 MHz, CDCl3) δ 7.16 – 7.12 (m, 2H), 6.63 – 6.57 (m, 3H), 5.44-5.31 (m, 2H), 3.25 – 3.19 (m, 2H), 2.83 (s, 3H), 2.0 (q, 2H), 1.60 –1.52 (m, 5H).

[0041] Example 7

[0042] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), phenylmethyl sulfoxide (0.5 mmol), and toluene (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 7a (1 mmol) and 18-crown-6 ether (0.3 mmol). The reaction was stirred at 25 °C for 24 hours, and then separated by column chromatography. Z -Compound 7b, colorless liquid, yield 82%. E:Z = 3:97.

[0043] The 1H NMR spectrum data of compound 7b are as follows: 1 H NMR(400 MHz, CDCl3) δ 7.08-7.01 (m, 2H), 6.91 – 6.84 (m, 2H), 5.43– 5.28 (m, 2H), 2.55 (t, J = 7.6 Hz, 2H), 2.25 (t, J = 7.4 Hz, 2H), 1.47 – 1.45(m, 3H). Example 8

[0044] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), dimethyl sulfoxide (0.5 mmol), and N,N-dimethylacetamide (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 h. Then, terminal olefin 8a (1 mmol) and 18-crown-6 ether (0.3 mmol) were added, and the reaction was stirred at 25 °C for 12 h. The mixture was then purified by column chromatography to obtain compound 8b as a colorless liquid with a yield of 95%.

[0045] The 1H NMR spectrum data of compound 8b are as follows: 1H NMR (400 MHz, CDCl3) δ 7.30 – 7.15 (m, 5H), 5.49 – 5.47 (m, 1H), 2.77-2.69 (m, 1H), 2.29 – 2.22 (m, 1H), 2.19 – 2.07 (m, 2H), 2.04 – 1.91 (m,2H), 1.82-1.73 (m, 1H), 1.70 (s, 3H). Example 9

[0046] Under a nitrogen atmosphere at room temperature, KN(SiMe3)2 (0.25 mmol), phenylmethyl sulfoxide (0.3 mmol), and toluene (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 hours. Then, dibenzo-18-crown-6 ether (0.3 mmol) and terminal olefin 9a (1 mmol) were added, and the reaction was stirred at 25 °C for 24 h. The mixture was then purified by column chromatography to obtain compound 9b, a colorless liquid, with a yield of 95%.

[0047] The 1H NMR spectrum data of compound 9b are as follows: 1 H NMR (400 MHz, CDCl3) δ 5.13-5.10 (m, 1H), 2.29-2.24 (m, 1H), 2.19 –1.98 (m, 2H), 2.02-1.98 (m, 1H), 1.86 (td, J = 5.6, 1.6 Hz, 1H), 1.59 (q, J = 2.0Hz, 3H), 1.19 (s, 3H), 1.08 (d, J = 8.4 Hz, 1H), 0.76 (s, 3H), Example 10

[0048] Under a nitrogen atmosphere at room temperature, KN(SiMe3)2 (0.25 mmol), N-phenylmethyl sulfoxide (0.3 mmol), and N,N-dimethylacetamide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 10a (1 mmol). The reaction was then stirred at 25 °C for 12 hours, and the mixture was purified by column chromatography to obtain the desired product. E - Compound 10b, colorless liquid, yield 90%. E:Z = 99:1.

[0049] The 1H NMR spectrum data of compound 10b are as follows: 1 H NMR(400 MHz, CDCl3) δ 7.35 – 7.32 (m, 2H), 7.30-7.26 (m, 2H), 7.19– 7.16 (m, 1H), 6.37 (dt, J = 16.0, 1.5 Hz, 1H), 6.26 (dt, J = 15.8, 6.3 Hz, 1H),2.25 – 2.20 (m, 1H), 1.09 (t, J = 7.5 Hz, 3H) Example 11

[0050] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), phenylmethyl sulfoxide (0.3 mmol), and tetrahydrofuran (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 12a (1 mmol). The reaction was then stirred at 25 °C for 3 hours, and compound 12b was obtained by column chromatography as a colorless liquid with a yield of 90%. E:Z = 99:1.

[0051] The 1H NMR data of compound 11b are as follows 1 H NMR (400 MHz, CDCl3) δ 7.54 – 7.51 (m, 2H), 7.39 – 7.35 (m, 6H), 7.30 – 7.23 (m, 2H), 6.84 (d, J = 1.6 Hz, 1H), 2.28 (d, J = 1.2 Hz, 3H). Example 12

[0052] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), phenylmethyl sulfoxide (0.5 mmol), and toluene (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 12a (1 mmol). The reaction was then stirred at 25 °C for 24 hours, and the product was obtained by column chromatography. E - Compound 12b, white solid, yield 90%. E:Z = 97:3.

[0053] The 1H NMR spectrum data of compound 12b are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.38 (t, J = 0.9 Hz, 1H), 7.30-7.27 (m, 4H), 7.24-7.23 (m, 2H), 7.19 – 7.14 (m, 1H), 2.20 (d, J = 1.6 Hz, 3H), 1.63 (s, 4H), 1.26 (s, 6H), 1.23 (s, 6H). Example 13

[0054] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), N,N-dimethylformamide (3 mmol), and toluene (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 13a (1 mmol). The reaction was then stirred at 25°C for 10 hours, and the product was obtained by column chromatography. Z -Compound 13b, white solid, yield 90%. E:Z >99:1.

[0055] The 1H NMR spectrum data of compound 13b are as follows: 1 H NMR(400 MHz, CDCl3) δ 7.35 – 7.32 (m, 2H), 7.25-7.22 (m, 5H), 7.21– 7.13 (m, 3H), 5.77 (dq, J = 8.6, 1.4 Hz, 1H), 3.95 (d, J = 12.8 Hz, 1H), 3.21-3.15 (m, 1H), 3.12 (d, J = 12.8 Hz, 1H), 2.94-2.89 (m, 1H), 2.10 (q, J = 8.8 Hz, 1H), 2.03 (d, J = 1.2 Hz, 3H), 1.99-1.91 (m, 1H), 1.79-1.65 – 1.64 (m, 3H). Example 14

[0056] Potassium tert-butoxide (0.25 mmol), N,N-diethylformamide (3 mmol), and tetrahydrofuran (2 mL) were added to a dry reaction tube at room temperature under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.5 hours, followed by the addition of terminal olefin 14a (1 mmol). The reaction was then stirred at 25 °C for 10 hours, and the product was obtained by column chromatography. Z - Configuration 14b, white solid, yield 78%.

[0057] The 1H NMR spectrum data of compound 14b are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.24 – 7.17 (m, 7H), 6.96 – 6.94 (m, 2H), 3.43 (s, 2H), 2.43 – 2.33 (m, 4H), 2.26 (t, J = 5.6 Hz, 2H), 2.07 – 2.04 (m, 2H), 1.85 (s, 3H).

[0058] Example 15

[0059] Under a nitrogen atmosphere at room temperature, KNH2 (0.25 mmol), N,N-diethylformamide (2 mmol), and N,N-dimethylformamide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N - Configurational mixture of olefins E / N -14a ( E:Z The mixture was stirred at 0 °C for 6 h (ratio 58:42) and then purified by column chromatography to obtain compound 14b as a colorless liquid, with a yield of 95%. E:Z = 99:1.

[0060] The 1H NMR spectrum data of compound 14b are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.46 (d, J = 2.4 Hz, 1H), 8.33 (dd, J = 4.8, 1.6Hz, 1H), 7.54 (dt, J = 8.0, 2.0 Hz, 1H), 7.11 (dd, J = 8.0, 4.8 Hz, 1H), 6.31 –6.19 (m, 2H), 1.82 (d, J= 5.2 Hz, 1H). Example 14

[0061] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), phenylmethyl sulfoxide (0.3 mmol), and diethyl ether (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N - Configurational mixture of olefins E / N -14a ( E:Z = 66:34)(1 mmol), after stirring at 0 °C for 24 h, compound 14b was separated by column chromatography as a colorless liquid with a yield of 88%. E:Z = 98:2.

[0062] The 1H NMR spectrum data of compound 14b are as follows: 1 H NMR (400 MHz, CDCl3) δ 6.99 (d, J = 5.2 Hz, 1H), 6.84 (dd, J = 5.0, 3.4Hz, 1H), 6.76 (d, J = 3.2 Hz, 1H), 6.59 – 6.36 (m, 1H), 6.00 (dq, J = 15.6, 6.7Hz, 1H), 1.77 (dd, J = 6.8, 1.6 Hz, 3H); Example 15

[0063] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (0.25 mmol), N,N-dimethylformamide (0.3 mmol), and tetrahydrofuran (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N -A mixture of olefins 11a (1 mmol) with different configurations was reacted with stirring at 25 °C for 24 h, followed by column chromatography to obtain... E - Compound 11b, a colorless liquid, in 89% yield. E:Z >99:1.

[0064] The 1H NMR spectrum data of compound 15b are as follows: 1H NMR(400 MHz, CDCl3) δ 7.27-7.23 (m, 2H), 6.84 – 6.70 (m, 2H), 6.33(dq, J = 15.7, 1.8 Hz, 1H), 6.08 (dq, J = 15.7, 6.6 Hz, 1H), 3.78 (s, 3H), 1.85(dd, J = 6.6, 1.8 Hz, 3H). Example 16

[0065] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (1.2 mmol), N,N-dimethylformamide (1.5 mmol), and N,N-dimethylacetamide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N -A mixture of olefins 16a (1 mmol) with different configurations was reacted with stirring at 25 °C for 24 h, followed by column chromatography to obtain... E - Compound 16b, a colorless liquid, in 89% yield. E:Z = 97:3.

[0066] The 1H NMR spectrum data of compound 16b are as follows: 1 H NMR (400 MHz, CDCl3) δ 6.85 – 6.82 (m, 3H), 6.31 (dq, J = 15.7, 1.7Hz, 1H), 6.07 (dq, J = 15.7, 6.6 Hz, 1H), 5.57 (s, 1H), 3.88 (s, 3H), 1.85 (dd, J = 6.8, 1.8 Hz, 3H). Example 17

[0067] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (1.2 mmol), N,N-dimethylformamide (0.5 mmol), and toluene (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N -A mixture of olefins 17a (1 mmol) with different configurations was reacted with stirring at 25 °C for 24 h, followed by column chromatography to obtain... E - Configuration 17b, colorless liquid, yield 89%. E:Z= 99:1.

[0068] The 1H NMR spectrum data of compound 17b are as follows: 1 H NMR (400 MHz, CDCl3) δ 6.96 – 6.72 (m, 3H), 6.33 (dq, J = 15.6, 1.7Hz, 1H), 6.10 (dq, J = 15.7, 6.6 Hz, 1H), 3.88 (s, 3H), 3.86 (s, 3H), 1.86 (dd, J = 6.6, 1.8 Hz, 3H). Example 18

[0069] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (1.2 mmol), N,N-dimethylformamide (0.5 mmol), and toluene (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... Z -17a (1 mmol), after being stirred at 25 °C for 24 h, was separated by column chromatography to obtain E - Compound 17b, a colorless liquid, in 92% yield. E:Z = 99:1.

[0070] Example 19

[0071] Under a nitrogen atmosphere at room temperature, potassium tert-butoxide (1.2 mmol), phenylmethyl sulfoxide (0.5 mmol), and dimethyl sulfoxide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N -A mixture of olefins 18a (1 mmol) with different configurations was reacted with stirring at 25 °C for 24 h, followed by column chromatography to obtain... E - Compound 18b, a colorless liquid, in 89% yield. E:Z = 98:2.

[0072] The 1H NMR spectrum data of compound 18b are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.22 (d, J= 8.4 Hz, 1H), 6.57-6.52 (m, 1H), 6.39 – 6.34 (m, 2H), 6.07 – 5.98 (m, 1H), 3.74 (s, 3H), 3.72 (s, 3H), 1.79(dd, J = 6.4, 1.6 Hz, 3H).

[0073] Example 20

[0074] Under a nitrogen atmosphere at room temperature, potassium hydroxide (0.25 mmol), dimethyl sulfoxide (0.5 mmol), and N,N-dimethylformamide (2 mL) were added to a dry reaction tube and stirred at room temperature for 0.5 hours. Then, [the mixture was further added...] E / N - Configurational mixture of olefins E / N -19a ( E:Z = 66:34)(1 mmol), after stirring at 25 °C for 12 h, compound 19b was separated by column chromatography as a colorless liquid with a yield of 88%. E:Z >99:1.

[0075] The 1H NMR spectrum data of compound 19b are as follows: H NMR (400 MHz, CDCl3) δ 7.36-7.33 (m, 2H), 7.30 – 7.26 (m, 2H), 7.20-7.16 (m, 1H), 6.36 (dd, J = 15.7, 1.4 Hz, 1H), 6.25-6.17 (m, 1H), 2.11-2.07 (m,1H), 1.76-1.68 (m, 1H), 0.94 (dd, J = 6.6, 1.4 Hz, 3H). Example 20

[0076] Under a nitrogen atmosphere at room temperature, KN(SiMe3)2 (0.25 mmol), N,N-diethylformamide (2 mL), and dimethyl sulfoxide (2 mL) were added to a dry reaction tube. The mixture was stirred at room temperature for 0.5 hours, and then... E / N - Configurational mixture of olefins E / N -20a ( E: Z The mixture was prepared by stirring at 25 °C for 3 h with a 50:50 ratio (1 mmol) and then separated by column chromatography to obtain compound 20b as a colorless liquid in 88% yield. E:Z= 99:1.

[0077] The 1H NMR spectrum data of compound 20b are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.24 – 7.16 (m, 6H), 7.13 – 7.07 (m, 4H), 6.38 – 6.29 (m, 1H), 6.15 (dt, J = 15.8, 6.7 Hz, 1H), 5.65 – 5.60 (m, 0H), 2.71-2.67 (m, 2H), 2.46 – 2.40 (m, 2H).

Claims

1. Catalyst A is used for the regio- and stereoselective synthesis of olefins, characterized in that: The catalyst A is K. + [O=X(R)R ’ The structural formula is: ； X is selected from C or S atoms; R, R ’ They are selected from hydrogen atoms, alkyl groups, or aryl groups, respectively.

2. The use according to claim 1, characterized in that: When X = C atoms, the structure of catalyst A is as follows: ； R and R mentioned in A ’ It is selected from one or two of methyl, ethyl, propyl, phenyl, and naphthyl groups respectively.

3. The use according to claim 1, characterized in that: When X = S atoms, the structure of catalyst A is as follows: ； In A, R is selected from one of methyl, ethyl, propyl, phenyl, and naphthyl.

4. A method for the regio- and stereoselective synthesis of inner olefins using catalyst A as described in claim 1, characterized in that: The general reaction formula is as follows: ； In the general reaction formula, when the reactants are open-ring olefins... When R'' is an alkyl chain with more than 2 carbon atoms, such as ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc., or aryl-substituted alkyl, such as ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc.; R''' and R'''' are hydrogen atoms, methyl, ethyl, etc., respectively. In the general reaction formula, when the reactants It is an exocyclic olefin or an exocyclic bridged olefin; The general formula for exocyclic olefin structures is , where R 1 R 2 , R 3 , R 4 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc. C1-C 20 Alkyl, C1-C 20 Aryl alkyl, aryl; m and n are each independently selected from 0 to 4; Alternatively, the structural formula of an exocyclic bridged cyclic olefin is: , where R 1 R 2 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc. C1-C 20 Alkyl, C1-C 20 The alkyl group is an aralkyl group, where m and n are each independently selected from 0 to 4; The activating agent is selected from one or a combination of two or more of 18-crown-6 ether, cyclohexyl-18-crown-6 ether, dicyclohexyl-18-crown-6 ether, benzo-18-crown-6 ether, or dibenzo-18-crown-6 ether.

5. A method for the regio- and stereoselective synthesis of inner olefins using catalyst A as described in claim 1, characterized in that: The general reaction formula is as follows: ； In the general reaction formula, when the reactant is an open-ring olefin... R'' is an aryl group such as phenyl, naphthyl, pyridyl, furanyl, or thiophene, or R'' is a methyl group substituted with aryl groups such as phenyl, naphthyl, pyridyl, furanyl, or thiophene; R''' and R'''' are hydrogen atoms, methyl, ethyl, or alkyl groups, respectively; The In the middle, R 1 Selected from aryl or substituted aryl groups such as phenyl, naphthyl, pyridyl, quinolinyl, piperazine, furanyl, thiophene, or imidazole; R 2 R 3 Each is independently selected from hydrogen atoms, methyl groups, ethyl groups, etc. (C1-C) 20 Alkyl, C1-C 20 Alkyl groups, aralkyl groups, or various substituted aryl groups; R 4 Selected from methyl, ethyl, propyl, or isopropyl; In the general reaction formula, when the reactant is an exocyclic olefin... The general formula for exocyclic olefins is The isomer is The Ar group is selected from aryl groups such as phenyl, naphthyl, furanyl, thiophene, or quinolinyl; the R group is selected from alkyl, aryl, acyl, ester, and halogen atoms such as fluorine, chlorine, bromine, and iodine; and n is selected from integers such as 0, 1, 2, 3, 4, 5, or 6.

6. A method for the regio- and stereoselective synthesis of inner olefins using catalyst A as described in claim 1, characterized in that: The general reaction formula is as follows: ； In the general reaction formula, the reactant open-ring olefin is E / Z -Olefin mixture or Z -olefin, R 1 Selected from aryl groups such as phenyl, naphthyl, pyridyl, quinolinyl, piperazine, furanyl, thiophene, or imidazole; R 2 R 3 R 4 Each is independently selected from unsubstituted or substituted methyl, ethyl, etc. C1-C 20 Alkyl and aralkyl substituted C1-C 20 alkyl.

7. The method according to claim 4, characterized in that: The In the middle, R 1 Selected from unsubstituted or substituted methyl, ethyl, etc. C1-C 20 Alkyl, heteroatom substituted C1-C 20 Alkyl, C1-C 20 Aryl alkyl, C3-C 20 Aryl alkyl groups with heteroatom substitution on the alkyl carbon chain, and C2-C groups with heterocyclic aryl substitution. 20 Alkyl; heteroatoms are selected from N, O, or S, and heterocyclic aryl groups are selected from pyridinyl, quinolinyl, piperazineyl, furanyl, thiopheneyl, or imidazolyl. R 2 R 3 Each is independently selected from hydrogen atoms, methyl groups, and ethyl groups.

8. The method according to any one of claims 4, 5 or 6, characterized in that: The K + The source is selected from one or a combination of two or more of potassium hydroxide, potassium tert-butoxide, potassium amino (KNH2) or bis-trimethylsilylamino potassium (KN(SiMe3)2).

9. The method according to any one of claims 4, 5 or 6, characterized in that: The organic solvent used in the reaction is selected from one or a combination of two or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, tetrahydrofuran, or diethyl ether.

10. The method according to any one of claims 4, 5 or 6, characterized in that: The reaction conditions are at a temperature of -50 to 120°C. Or, the stated The molar ratio of catalyst A to activating agent is 1:0.05-5:0.06-6; Or, the stated or The molar ratio of catalyst A is 1:0.05-5:.

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