A method for the coupling of olefins to form polysubstituted olefinic compounds

Abstract

The application belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing polysubstituted olefin compounds through olefin coupling. The method comprises the following steps: reacting compound A0 and compound B0 under the action of an imidazoline-2-imine rare earth metal complex and an activating agent boron salt to obtain a polysubstituted olefin compound shown in formula I. The synthesis method can obtain a series of polysubstituted olefin compounds in high yield and high cis-trans ratio, and has the advantages of simplicity, high efficiency, environmental friendliness, good substrate universality and wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing polysubstituted olefin compounds through olefin coupling. BACKGROUND

[0002] Catalytic C-H bond functionalization as a powerful strategy in organic synthesis chemistry and related fields has received extensive attention in the past few decades. Developing new catalysts that are better or complementary to existing catalysts to provide new synthetic methods and strategies has been a long-term research topic.

[0003] Olefins are widely present in drug molecules, natural products, and functional materials. The configuration (Z or E) of the double bond in the olefin molecule significantly affects the activity of the bioactive molecule and the performance of the material. Although the Lindlar reduction reaction and the Wittig reaction can synthesize olefin molecules with high E / Z stereoselectivity, the Lindlar reduction requires the use of noble metal palladium, and the substrate range is limited. The atom economy of the Wittig reaction is not high. Therefore, developing new methods for synthesizing olefins has important theoretical significance and application prospects. By activating the C(sp 3 )-H bond at the allylic position, olefin derivatives can be directly synthesized with high step and atom economy, which meets the development concept of green chemistry. Currently, the main strategies for allylic C(sp 3 )-H functionalization reactions are as follows:

[0004] (1) Palladium-catalyzed allylic C-H functionalization: This strategy uses a palladium complex and an external oxidant to activate the terminal olefin allylic C-H bond to form an electrophilic π-allyl palladium intermediate, which then couples with a nucleophile. White and Gong reported different catalytic systems to achieve the above conversion (J. Am. Chem. Soc. 2008, 130, 14090-14091, Acc. Chem. Res. 2020, 53, 2841-2854.).

[0005] (a) Allylic C-H activation of α-alkenes via electrophilic allyl-Pd(II) intermediate.

[0006]

[0007] (2) Allylic C-H functionalization catalyzed by cheap metals (mainly alkali metals and Fe, etc.): This strategy utilizes the weak interaction between metal and double bond to activate the allylic C-H bond of olefins, forming a nucleophilic allyl metal species, which then undergoes coupling with electrophilic reagents to generate the corresponding olefin derivatives. In 2023, Wang's group reported the allylic C-H functionalization of propylene and simple olefins catalyzed by cationic cyclopentadienyl iron dicarbonyl complexes. The addition of an external base removes the proton at the allylic position to generate a nucleophilic allyl metal species, which then undergoes addition reaction with aldehydes (Angew. Chem. Int. Ed. 2023, 62, e202216309.). Alkali metals, due to their strong basicity, can activate the allylic C-H bond through acid-base reaction (J. Am. Chem. Soc. 2017, 139, 4362-4365.).

[0008] (b) Allylic C-H functionalization ofalkenesvia nucleophilic allylmetalspecies.

[0009]

[0010] Although the allylic C(sp 3 ​)-H functionalization reactions have made the above-mentioned important progress, but there are still many key scientific issues in this field: (1) Due to the low reactivity of internal olefins, the carbon-hydrogen functionalization reaction involves cis-trans isomerization of double bonds in raw materials and products, which is very challenging and has few research reports (Acc. Chem. Res. 2020, 53, 841–2854. Page 2852 has the following comment: In addition, the alkene scope is restricted to α-alkenes, and future development toward internal alkenes (internal olefins) will be highly desired); (2) Coupling reagents are mostly highly active nucleophiles and electrophiles. There are few reports on olefins as coupling reagents, and the substrate universality is poor (Acc. Chem. Res. 2020, 53, 2841–2854. Page 2852 has the following comment: only partial soft nucleophiles show excellent reactivity toward allylic CH functionalization, but the oxidative coupling of allylic CH with hard nucleophiles has rarely beeninvestigated.Org.Lett.2018,20,7177–718).

[0011] Rare earth metals (REEs) are a collective term for 17 elements, including scandium, yttrium, and the lanthanides (La-Lu). REEs possess unique electronic structures and chemical properties that differ from those of main-group metals and late transition metals. Thanks to their strong heteroatom affinity and rapid migration and insertion into unsaturated double bonds, REE organic complexes have been successfully used in direct carbon-hydrogen functionalization reactions of heteroatom-containing substrates (such as pyridine, sulfide, amine, and imine) with alkenes and alkynes (Tetrahedron 2023, 135, 133323–133339). In addition to interactions between REE heteroatoms, REEs also exhibit weaker interactions with alkenes or aromatics. These weak interactions play an important role in controlling the activity and selectivity of hydrogen functionalization reactions of heteroatom substrates and olefin polymerization reactions.

[0012] The inventor's research group has developed a new type of imidazoline-2-imine rare earth metal cation complex catalyst in previous research. This type of complex can achieve C(sp) conversion of anisole, 2-methylanisole, pyridine, 2-methylpyridine and aniline substrates with high efficiency and high regioselectivity. 2 )-H and C(sp 3) -H alkylation reactions (Chem. Sci. 2023, 14, 3132-3139, Sci. China Chem. 2023, 66, 1804-1813, Chem. Eur. J. 2024, e202401014).

[0013] However, the activation of allylic or benzylic C-H bonds using rare earth metal-π interactions has not been discovered and reported. SUMMARY

[0014] The object of the present application is to provide a method for olefin cross-coupling and dimerization.

[0015] A method for olefin coupling to form a polysubstituted olefin compound, comprising the following steps: reacting compound A0 with compound B0 in the presence of an imidazoline-2-imine rare earth metal complex and an activating agent boron salt to obtain a polysubstituted olefin compound represented by formula I;

[0016]

[0017] wherein,

[0018] R 1 , R 0 are each independently selected from hydrogen, substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C4-C 10 cycloalkyl, trimethylsilyl, substituted or unsubstituted C6-C 10 aryl, wherein the substituents are selected from halogen, C1-C6 alkyl, C2-C 10 alkenyl, C1-C6 alkylthio, C6-C 10 aryl, phenoxy, C1-C6 alkyl substituted amino;

[0019] Alternatively, R 1 and R 0 are linked to form a substituted or unsubstituted C3-C 10 cycloalkyl, wherein the substituents are selected from C1-C6 alkyl;

[0020] R 2 is selected from hydrogen, C1-C4 alkyl, C6-C 10 aryl,

[0021] Alternatively, R 1 and R 2 are linked to form a substituted or unsubstituted C3-C 10 cycloalkyl, wherein the substituents are selected from C1-C6 alkyl;

[0022] R 3 is selected from hydrogen, C1-C 10 alkyl, C4-C10 Cycloalkyl, C6~C 10 Aryl,

[0023] Or, R 2 and R 3 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1 to C6 alkyl;

[0024] R 4 Selected from hydrogen, C1~C 10 alkyl;

[0025] R 5 Selected from substituted or unsubstituted C6~C 10 Aryl, ferrocene, wherein the substituent is selected from halogen, C1~C6 alkyl, C2~C 10 alkenyl, C1-C6 alkylthio, C6-C 10 Aryl, phenoxy, C1-C6 alkyl substituted amino, or two adjacent substituents connected to form a substituted or unsubstituted C4-C 20 Cycloalkyl, wherein the substituent is selected from C1-C6 alkyl and dimethyl tert-butylsilyl ether.

[0026] Preferably, the structural formula of the compound represented by Formula I is as shown in any one of Formula II to Formula VI:

[0027]

[0028]

[0029] Preferably, R 0 selected from hydrogen;

[0030] R 1 selected from hydrogen, substituted or unsubstituted C1-C7 alkyl, C6 cycloalkyl, trimethylsilyl, C6-C7 substituted or unsubstituted with 1-3 substituents 10 Aryl, wherein the substituent is selected from halogen, C1-C3 alkyl, C3 alkenyl, methylthio, phenyl, phenoxy, N,N-dimethylamino.

[0031] Preferably, R 2 Selected from hydrogen, phenyl;

[0032] and / or, R 3 Selected from hydrogen, C1-C3 alkyl, phenyl;

[0033] and / or, R 4 Selected from hydrogen and methyl.

[0034] Preferably, R 5 Selected from substituted or unsubstituted ethyl, substituted or unsubstituted C6~C 10aryl, ferrocene, the substituents are selected from F, Br, C1-C4 alkyl, phenyl, methylthio, N,N-dimethylamino, or two adjacent substituents are linked to form a substituted or unsubstituted C 11 cycloalkyl, wherein the substituents are selected from methyl, dimethyl tert-butyl silyl ether.

[0035] Preferably, R 1 and R 0 are linked to form a C6 cycloalkyl;

[0036] or, R 1 and R 2 are linked to form a C6-C7 cycloalkyl substituted or unsubstituted by 1-2 substituents, wherein the substituents are selected from C1-C3 alkyl;

[0037] or, R 2 and R 3 are linked to form a C4 cycloalkyl.

[0038] Preferably, the compound of formula I is selected from:

[0039]

[0040]

[0041]

[0042]

[0043] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0044]

[0045] wherein M is selected from Sc, Y;

[0046] m, n are independently selected from 1, 2, 3, 4, 5;

[0047] R 6 is selected from C1-C6 alkyl, substituted or unsubstituted C4-C 10 cycloalkyl, substituted or unsubstituted C6-C 10 aryl, wherein the substituents are C1-C6 alkyl, C6-C 10 aryl;

[0048] The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:(2-10);

[0049] The molar ratio of the compound B0 to the activator boron salt is 100:(2-10);

[0050] The molar ratio of the compound B0 to the compound A0 is 1: (0.5-100);

[0051] The solvent of the reaction is an organic solvent;

[0052] The temperature of the reaction is 10-120℃, and the time is 12-24h.

[0053] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0054]

[0055]

[0056] The activating agent boron salt is selected from triphenylcarbenium tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, N, N-dimethylanilinium tetrakis(pentafluorophenyl)borate;

[0057] The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:10;

[0058] The molar ratio of the compound B0 to the activating agent boron salt is 100:10;

[0059] The molar ratio of the compound B0 to the compound A0 is 1:3;

[0060] The solvent of the reaction is one or more than two kinds of mixture of halogenated hydrocarbons, aromatic hydrocarbons, ethers, alcohols, aliphatic hydrocarbons, preferably one or more than two kinds of mixture of methanol, dichloromethane, n-hexane, diethyl ether, o-xylene, m-xylene, p-xylene, mesitylene, trifluorotoluene, chlorobenzene, benzene, toluene;

[0061] The temperature of the reaction of step (1) is 100℃, and the time is 12h.

[0062] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0063] The activating agent boron salt is selected from triphenylcarbenium tetrakis(pentafluorophenyl)borate;

[0064] The solvent of the reaction is selected from toluene.

[0065] Definitions of terms used in connection with the present invention: unless otherwise indicated, the initial definition of a group or term provided herein applies throughout the specification; for terms not specifically defined herein, the meaning given to them by one of ordinary skill in the art in light of the disclosure and context will prevail.

[0066] "Substituted" means that a hydrogen atom in a molecule is replaced with a different atom or molecule. "Substituted" can mean replaced with one group, or replaced with at least two groups.

[0067] The minimum and maximum number of carbon atoms in a hydrocarbon group is indicated by a prefix, e.g., the prefix C a -C b Alkyl indicates any alkyl group of from "a" to "b" carbon atoms. Thus, for example, "C1-C4 alkyl" refers to an alkyl group containing from 1 to 4 carbon atoms.

[0068] "Alkyl" refers to a saturated hydrocarbon chain having the specified number of members. For example, C1-C6 alkyl refers to an alkyl group having from 1 to 6 members, e.g., from 1 to 4 members. The alkyl group can be straight or branched. Representative branched alkyl groups have one, two, or three branches. The alkyl group can be optionally substituted with one or more substituents as defined herein. Alkyl includes methyl, ethyl, propyl (n-propyl and isopropyl), butyl (n-butyl, isobutyl, and t-butyl), pentyl (n-pentyl, isopentyl, and neopentyl), and hexyl. The alkyl group can also be part of other groups, e.g., C1-C6 alkoxy.

[0069] "Cycloalkyl" refers to a saturated or partially saturated cyclic group having from 3 to 14 carbon atoms and no ring heteroatoms and having a single ring or multiple rings (including fused, bridged, and spiro ring systems). For multiple ring systems having both aromatic and non-aromatic rings free of ring heteroatoms, the term "cycloalkyl" applies when the point of attachment is to a non-aromatic carbon atom (e.g., 5,6,7,8,- tetrahydronaphthalen-5-yl). The term "cycloalkyl" includes cycloalkenyl groups, such as cyclohexenyl. Examples of cycloalkyl groups include, e.g., adamantyl, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclopentenyl, and cyclohexenyl. Examples of cycloalkyl groups including polycycloalkyl ring systems are bicyclohexyl, bicyclopentyl, bicyclooctyl, and the like. Two such bicycloalkyl polycyclic structures are exemplified and named below: Bicyclohexyl and Bicyclohexyl.

[0070] "Alkenyl" refers to a straight or branched hydrocarbon group having from 2 to 10 carbon atoms and in some embodiments from 2 to 6 carbon atoms or from 2 to 4 carbon atoms and having at least 1 site of vinyl unsaturation (>C=C<). For example, (Ca-Cb)alkenyl refers to an alkenyl group having from a to b carbon atoms and is intended to include, for example, ethenyl, propenyl, isopropenyl, 1,3- butadienyl, and the like.

[0071] "Halogen" is fluorine, chlorine, bromine, or iodine.

[0072] "R a and Rb Connected to form a ring "refers to R a and R b There is at least one atom connected by a chemical bond in each of the two atoms, so that R a and R b The atoms or chains of atoms that are connected together are part of the ring structure and the backbone of the ring is R a and R b Together they form a ring.

[0073] "Alkylthio" refers to a functional group formed by removing a hydrogen atom attached to a sulfur atom in a thiol compound having a specified number of carbon atoms.

[0074] The hydrogen atoms in the compounds of the present invention may be various isotopes of hydrogen, such as protium ( 1 H), deuterium (2H), or tritium ( 3 H).

[0075] In the present invention, the abbreviations of the substituents are as follows: Ph is phenyl, Me is methyl, Et is ethyl, i Pr is isopropyl, i Bu is an isobutyl group, Ad is an adamantyl group, Cy is a cyclohexyl group, OTBS is a dimethyl tert-butylsilyl ether, and TMS is a trimethylsilyl group.

[0076] The present invention provides a new method for the efficient catalytic cross-coupling and dimerization of olefins using rare earth organic complexes, and allows for the highly selective synthesis of a series of olefin derivatives. Compared with the prior art, the present invention has the following advantages:

[0077] 1. Develop a novel imidazoline-2-imine rare earth metal complex catalyst for the hydrocarbon alkylation of β-methylstyrene and toluene substrates, achieving high yields and high cis-trans selectivity for the synthesis of polysubstituted olefins and their analogs, with good substrate universality.

[0078] 2. This method was used for the first time to demonstrate that imidazoline-2-imine rare earth metal complex catalysts can achieve carbon-hydrogen bond activation reactions through rare earth metal-π interactions.

[0079] 3. The product is easy to separate from the catalyst and raw materials; the reaction system is simple and clean, in line with the green chemical atom economy;

[0080] The present invention utilizes imidazoline-2-imine rare earth metal catalyst to catalyze the allylic hydrocarbon alkylation reaction, thereby achieving the synthesis of polysubstituted olefin compounds with high yield and high cis-trans ratio. The method is simple, efficient, environmentally friendly, has good substrate universality, and has broad application prospects.

[0081] Obviously, based on the above contents of the present invention, according to common technical knowledge and customary means in this field, without departing from the above basic technical ideas of the present invention, other various forms of modifications, replacements or changes can be made.

[0082] The following further describes the above content of the present invention in detail through specific embodiments in the form of examples. However, this should not be construed as limiting the scope of the above subject matter of the present invention to the following examples. All technologies implemented based on the above content of the present invention fall within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Fig. 1 : Single crystal structure of catalyst Sc-2.

[0084] Fig. 2 : Single crystal structure of catalyst Sc-4.

[0085] Fig. 3 : Single crystal structure of catalyst Sc-11.

[0086] Fig. 4 : Single crystal structure of catalyst Sc-13. DETAILED DESCRIPTION

[0087] The raw materials and equipment used in this invention are all known products and were purchased commercially. The reactions and product processing described in the examples were performed using Schlenk tube technology and an argon glove box in an anhydrous and oxygen-free environment. All solvents and reagents used were anhydrous and oxygen-free.

[0088] Example 1: Catalyst Synthesis

[0089]

[0090] Step 1: In a glove box, Sc(CH2C6H4NMe2-o)3 (0.5 mmol, 1.0 equiv) and imidazoline-2-imide (0.5 mmol, 1.0 equiv) were dissolved in tetrahydrofuran. The mixture was stirred at room temperature for 12 hours. The solvent was removed under vacuum, and the solid was dissolved in toluene. The mixture was filtered and the filtrate was collected. The solvent was removed under vacuum, and the solid was washed with n-hexane. The remaining solid was dissolved in boiling n-hexane. After cooling to room temperature, a large amount of product precipitated. The product was filtered, the solid was washed with n-hexane, and dried under vacuum to obtain catalysts Sc-1-Sc-12. Representative catalyst characterization data are as follows:

[0091]

[0092] Sc-2(C 53 H 76 N5Sc) Synthesis method: See Step 1. (white solid, 311.0 mg, 75% yield).1 H NMR (400 MHz, Benzene-d6) δ 7.19 (s, 2H), 7.09 (s, 2H), 7.05 - 6.97 (m, 4H), 6.83 - 6.81 (m, 2H), 6.75 (d, J = 8.0 Hz, 2H), 3.41 (s, 2H), 2.99 - 2.77 (m, 4H), 2.33 (s, 6H), 1.97 (s, 6H), 1.63 (d, J = 5.8 Hz, 8H), 1.47 (s, 6H), 1.35 (s, 2H), 1.30 (d, J = 7.0 Hz, 12H), 1.22 (d, J = 6.8 Hz, 12H), 1.01 (d, J = 6.6 Hz, 6H).

[0093]

[0094] Sc-4(C 67 H 92 N5Sc) was synthesized according to step one. (White solid, 354.0 mg, 70% yield). 1 H NMR (400 MHz, Benzene-d6) δ 7.43 (s, 2H), 7.35 (d, J = 7.8 Hz, 2H), 7.05 - 6.96 (m, 4H), 6.88 - 6.57 (m, 4H), 3.48 (s, 2H), 2.99 (s, 2H), 2.34 (s, 6H), 2.12 - 1.97 (m, 20H), 1.92 - 1.56 (m, 18H), 1.47 (s, 6H), 1.38 (t, J = 10.8 Hz, 2H), 1.33 - 1.16 (m, 18H), 1.08 (d, J = 6.8 Hz, 6H).

[0095]

[0096] Sc-11(C 91 H 88 N5Sc) was synthesized according to step one. (White solid, 310.0 mg, 50% yield). 1H NMR (400 MHz, Benzene-d6) δ 7.89 (d, J = 7.6 Hz, 3H), 7.82 - 7.74 (m, 3H), 7.49 (t, J = 7.6 Hz, 3H), 7.40 - 7.31 (m, 4H), 7.16 (s, 13H), 7.03 (t, J = 4.0 Hz, 10H), 6.98 (t, J = 6.8 Hz, 3H), 6.89 - 6.84 (m, 6H), 6.78 - 6.73 (m, 4H), 6.68 - 6.55 (m, 5H), 5.88 (s, 2H), 4.56 (s, 2H), 2.60 (p, J = 6.8 Hz, 2H), 2.38 (s, 6H), 2.23 (d, J = 10.4 Hz, 2H), 1.96 (d, J = 10.2 Hz, 2H), 1.66 (s, 6H), 1.36 (s, 2H), 1.04 (d, J = 6.8 Hz, 10H).

[0097]

[0098] Step two: In a glove box, ScCl3-(THF)3 (0.5 mmol, 1.0 equiv) and LiCH2SiMe3 (0.5 mmol, 1.0 equiv) were dissolved in THF, stirred at room temperature for 2 hours, then the imidazoline-2-imine THF solution was added, the reaction mixture was continued to react at room temperature for 12 hours, the solvent was removed under vacuum, the solid was dissolved in n-hexane, filtered, the filtrate was concentrated, the solid was recrystallized from THF / pentane (1:2, v / v) at -30 °C to give colorless crystals. Yield 40%.

[0099] The solid was dissolved in THF, C3H5MgCl (2 equiv) THF solution was added, reacted at room temperature for 12 hours, the solvent was removed under vacuum, the solid was dissolved in n-hexane, filtered, the filtrate was concentrated, the solid was recrystallized from THF / pentane (1:2, v / v) at -30 °C to give colorless crystals Sc-13, filtered, the solid was washed with n-hexane, dried under vacuum, yield 50%.

[0100] 1 H NMR (400 MHz, Benzene-d6) δ 7.22 - 7.13 (m, 2H), 7.14 (d, J = 6.6 Hz, 4H), 6.62 - 6.38 (m, 2H), 3.34 (q, J = 6.8 Hz, 4H), 3.12 (d, J = 6.4 Hz, 4H), 2.85 (d, J = 12.2 Hz, 8H), 1.56 (s, 6H), 1.48 (d, J = 6.8 Hz, 12H), 1.22 (d, J = 7.0 Hz, 12H), 1.13 - 1.08 (m, 4H).

[0101]

[0102] Step 3: In a glove box, Sc(CH2TMS)3·2THF (0.5 mmol, 1.0 equiv) and imidazoline-2-imide (0.5 mmol, 1.0 equiv) were dissolved in tetrahydrofuran and reacted at room temperature for 12 hours. The solvent was removed under vacuum, and the solid was dissolved in n-hexane, filtered, concentrated, and recrystallized at –30°C to obtain colorless crystals. The crystals were filtered and dried to obtain catalysts Sc-15-Sc-17. Characterization data of representative catalysts are as follows:

[0103]

[0104] Sc-15(C 47 H 82 N3OScSi2) Synthesis method: See Step 3. (White crystals, 282.0 mg, 70% yield). 1 HNMR (400MHz, Benzene-d6) δ6.93(d,J=3.6Hz,2H),6.83(d,J=7.6Hz,4H),5.71(s,2H),3.15(t,J=6.8Hz,4H),2.69–2.65(m,4H),1.72–1.69( m,4H),1.64–1.54(m,4H),1.51–1.46(m,4H),1.38–1.27(m,4H),0.91(t,J=7.4Hz,16H),0.61(t,J=7.4Hz,12H),0.00(s,18H),-0.56(s,4H).

[0105] Example 2: Preparation of polysubstituted olefin compounds D1-D50

[0106] In a glove box, imidazoline-2-imine rare earth metal complex catalyst Sc-2 (8.3 mg, 0.01 mmol) and triphenylcarbon tetrakis(pentafluorophenyl)borate (9.2 mg, 0.01 mmol) were weighed into a bottle, toluene (1.0 mL) was added, and the mixture was activated at room temperature for 10 minutes. β-Methylstyrene A (35.4 mg, 0.3 mmol) and styrene B (10.4 mg, 0.1 mmol) were added, and the mixture was removed from the glove box and reacted at 100°C for 12 hours. The reaction solution was directly purified by silica gel column chromatography and eluted with petroleum ether to obtain product D. The cis-trans ratio of the product was determined by analysis using a nuclear magnetic resonance spectrometer. The reaction structure is as follows:

[0107]

[0108] The structures of compounds D1-D50 prepared according to the above method (the reaction conditions are the same, the difference is that the specific raw materials are selected according to the structure of the compound), the yields and cis-trans ratios are as follows:

[0109]

[0110]

[0111] Important product characterization data are as follows:

[0112] Product D1: Pent-1-ene-1,5-diyldibenzene(D1)(C 17 H 18 )colorless oil; 21.1mg, 95% yield, E / Z=6:1, 1 H NMR(400MHz,Chloroform-d)majorEisomer:δ7.34–7.24(m,6H),7.18–7.15(m,4H),6.47– 6.31(m,1H),6.39–6.17(m,1H),2.66–2.60(m,2H),2.27–2.17(m,2H),1.81–1.74(m,2H).

[0113] Product D5:

[0114] 1-Isopropyl-4-(5-phenylpent-1-en-1-yl)benzene(D5)(C 20 H 24 )colorlessoil; 26.2mg, 99% yield, E / Z=9:1, 1 H NMR(400MHz,Chloroform-d)major E isomer: δ7.28(d,J=1.6Hz,3H),7.21–7.13(m,6H),6.40–6.33(m,1H),6.22–6.14(m,1H),2.93–2 .84(m,1H),2.68–2.64(m,2H),2.28–2.16(m,2H),1.83–1.75(m,2H),1.23(d,J=6.8Hz,6H). Product D6:

[0115] 2-(5-Phenylpent-1-en-1-yl)naphthalene(D6)(C 21 H 20) colorless oil; 22.3 mg, 82% yield, E / Z = 3.3: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.80 - 7.76 (m, 3H), 7.68 (d, J = 1.8 Hz, 1H), 7.61 - 7.56 (m, 1H), 7.45 - 7.40 (m, 2H), 7.31 - 7.29 (m, 2H), 7.24 (d, J = 1.6 Hz, 2H), 6.59 - 6.54 (m, 1H), 6.41 - 6.34 (m, 1H), 2.74 - 2.69 (m, 2H), 2.36 - 2.28 (m, 2H), 1.87 (td, J = 7.4, 1.6 Hz, 2H).

[0116] Product D7:

[0117] 1 -(5-Phenylpent- 1 -en- 1 -yl)-4-[(E)-prop- 1 -en- 1 -yl]benzene (D7) (C 20 H 22 ) colorless oil; 24.4 mg, 93% yield, E / Z = 10: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.31 - 7.22 (m, 5H), 7.22 - 7.15 (m, 4H), 7.13 - 7.11 (m, 1H), 6.42 - 6.33 (m, 2H), 6.26 - 6.17 (m, 2H), 2.69 - 2.64 (m, 2H), 2.31 - 2.17 (m, 2H), 1.90 - 1.84 (m, 3H), 1.83 - 1.76 (m, 2H).

[0118] Product D9:

[0119] 1 -Phenoxy-4-(5-phenylpent- 1 -en- 1 -yl)benzene (D9) (C 23 H 22 O) colorless oil; 25.2 mg, 80% yield, E / Z = 6.3: 1, 1H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.34 - 7.26 (m, 6 H), 7.21 - 7.17 (m, 3 H), 7.09 (d, J = 7.6 Hz, 1 H), 7.01 - 6.97 (m, 2 H), 6.95 - 6.92 (m, 2 H), 6.36 (d, J = 15.8 Hz, 1 H), 6.16 - 6.12 (m, 1 H), 2.68 - 2.64 (m, 2 H), 2.27 - 2.19 (m, 2 H), 1.82 - 1.76 (m, 2 H).

[0120] Product D10: Methyl [4-(5-phenylpent-1-en-1-yl)phenyl] sulfane (D10) (C 18 H 20 S) colorless oil; 24.2 mg, 90% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.32 - 7.26 (m, 4 H), 7.21 - 7.18 (m, 5 H), 6.35 (d, J = 15.8, 1 H), 6.24 - 6.17 (m, 1 H), 2.72 - 2.63 (m, 2 H), 2.48 (s, 3 H), 2.31 - 2.19 (m, 2 H), 1.85 - 1.79 (m, 2 H).

[0121] Product D11: N,N-Dimethyl-4-(5-phenylpent-1-en-1-yl)aniline (D11) (C 19 H 23 N) colorless oil; 18.8 mg, 71% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.35 - 7.25 (m, 5 H), 7.24 - 7.19 (m, 4 H), 6.71 (d, J = 8.8 Hz, 2 H), 6.37 - 6.32 (d, J = 15.8 Hz, 1 H), 6.10 - 6.02 (m, 1 H), 2.97 (s, 6 H), 2.71 - 2.67 (m, 2 H), 2.28 - 2.22 (m, 2 H), 1.86 - 1.77 (m, 2 H. Product D12:

[0122] 1-Fluoro-4-(5-phenylpent-1-en-1-yl)benzene (D12) (C17 H 17 F) colorless oil; 13 mg, 54% yield, E / Z = 18: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.32 - 7.27 (m, 4H), 7.20 (d, J = 7.0 Hz, 3H), 6.98 (t, J = 8.8 Hz, 2H), 6.36 (d, J = 16.0 Hz, 1H), 6.18 - 6.11 (m, 1H), 2.71 - 2.65 (m, 2H), 2.28 - 2.20 (m, 2H), 1.85 - 1.77 (m, 2H).

[0123] Product D14:

[0124] 1-Chloro-4-(5-phenylpent-1-en-1-yl)benzene (D14) (C 17 H 17 Cl) colorless oil; 12.3 mg, 48% yield, E / Z = 7: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.32 - 7.28 (m, 2H), 7.26 (s, 4H), 7.22 - 7.19 (m, 3H), 6.37 - 6.32 (m, 1H), 6.25 - 6.18 (m, 1H), 2.71 - 2.65 (m, 2H), 2.30 - 2.21 (m, 2H), 1.85 - 1.78 (m, 2H).

[0125] Product D19:

[0126] 1-Iodo-4-(5-phenylpent-1-en-1-yl)benzene (D19) (C 17 H 17 I) colorless oil; 12.5 mg, 36% yield, E / Z = > 19: 1, 1 H NMR (400 MHz, Chloroform-d) δ

[0127] 7.64 - 7.58 (m, 2H), 7.29 (q, J = 7.4 Hz, 3H), 7.21 - 7.19 (m, 3H), 7.10 - 7.05 (m, 2H), 6.37 - 6.11 (m, 2H), 2.71 - 2.64 (m, 2H), 2.24 (q, J = 7.0 Hz, 2H), 1.86 - 1.76 (m, 2H).

[0128] Product D20:

[0129] (3-Methylpent-1-ene-1,5-diyl)dibenzene (D20) (C 18 H 20 ) colorless oil; 20.1 mg, 85% yield, E / Z = 3.7: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.39 - 7.34 (m, 2H), 7.32 - 7.28 (m, 3H), 7.23 - 7.16 (m, 5H), 6.38 (d, J = 15.6 Hz, 1H), 6.16 - 6.10 (m, 1H), 2.68 - 2.61 (m, 3H), 2.38 - 2.31 (m, 1H), 1.76 - 1.70 (m, 2H), 1.12 (d, J = 6.8 Hz, 3H). Product D22:

[0130] (3-Propylpent-1-ene-1,5-diyl)dibenzene (D22) (C 20 H 24 ) colorless oil; 14.8 mg, 56% yield, E / Z = 6.3: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.39 (d, J = 7.3 Hz, 2H), 7.33 - 7.28 (m, 3H), 7.24 - 7.16 (m, 5H), 6.37 (d, J = 15.8 Hz, 1H), 6.01 (dd, J = 15.8, 9.1 Hz, 1H), 2.73 - 2.66 (m, 1H), 2.60 - 2.53 (m, 1H), 2.23 - 2.16 (m, 1H), 1.83 - 1.76 (m, 1H), 1.69 - 1.60 (m, 1H), 1.45 - 1.29 (m, 4H), 0.89 (t, J = 7.0 Hz, 3H).

[0131] Product D26: Dec-4-en-1-ylbenzene(D26)(C 16 H 24 )colorless oil;7.6mg,35%yield,E / Z=>19:1, 1 H NMR(400MHz,Chloroform-d)δ7.30–7.26(m,2H),7.19–7.16(m,3H),5.44–5.39(m,2H),2.63–2.58(m,2H),2.04–1.96(m,4H),1.70–1.65(m,2H),1.36–1.28(m,6H),0.87(t,J=7.2Hz,3H).

[0132] 产品D27:

[0133] (5-Cyclohexylpent-4-en-1-yl)benzene(D27)(C 17 H 24 )colorless oil;10.5mg,46%yield,E / Z=>19:1, 1 H NMR(400MHz,Chloroform-d)δ7.30–7.26(m,2H),7.20–7.15(m,3H),5.37(q,J=2.6Hz,2H),2.63–2.56(m,2H),2.05–1.99(m,2H),1.94–1.85(m,1H),1.75–1.66(m,6H),1.26(d,J=5.6Hz,4H),1.09–0.99(m,2H).

[0134] 产品D28: Hex-2-ene-1,6-diyldibenzene(D28)(C 19 H 22 )colorless oil;13.0mg,52%yield,E / Z=>19:1, 1H NMR(400MHz,Chloroform-d)δ7.37(d,J=7.2Hz,1H),7.32–7.25(m,6H),7.23–7.14(m,8H),6.38(d,J=15.8Hz,1H),6.13(dd,J=15.8,8.0Hz,1H),5.64–5.47(m,2H),3.34(d,J=6.2Hz,2H),2.71–2.57(m,3H),2.38–2.31(m,1H),2.07(q,J=7.0Hz,2H),1.75–1.67(m,3H),1.12(d,J=6.8Hz,2H).

[0135] 产品D29:

[0136] [2-(2-Benzylidenecyclobutyl)ethyl]benzene(D29)(C 19 H 20 )colorless oil;24.6mg,99%yield,E / Z=4:1, 1 H NMR(400MHz,Chloroform-d)major E isomer:δ7.27–7.21(m,5H),7.14–7.10(m,5H),6.06(s,1H),3.35–3.34(m,1H),2.98–2.96(m,1H),2.88–2.84(m,1H),2.79–2.71(m,1H),2.70–2.65(m,1H),2.56–2.50(m,1H),2.29–2.24(m,1H),2.16–2.08(m,1H),1.82–1.76(m,2H).

[0137] 产品D30:

[0138] (2-Methylpent-1-ene-1,5-diyl)dibenzene(D30)(C 18 H 20 )colorless oil;14.4mg,62%yield,E / Z=4:1, 1H NMR(400MHz,Chloroform-d)major E isomer:δ7.26(t,J=7.4Hz,5H),7.17–7.11(m,5H),6.29(s,1H),2.66(t,J=7.8Hz,1H),2.60(t,J=7.8Hz,2H),2.28(dd,J=9.6,6.4Hz,2H),1.88(s,3H),1.82(t,J=7.8Hz,2H).

[0139] 产品D31:

[0140] 1-Methyl-2-(5-phenylpent-4-en-1-yl)benzene(D31)(C 18 H 20 )colorless oil;14.2mg,60%yield,E / Z=4.4:1, 1 H NMR(400MHz,Chloroform-d)major E isomer:δ7.37–7.33(m,2H),7.23–7.18(m,2H),7.15–7.10(m,5H),6.42(d,J=15.8Hz,1H),6.29–6.22(m,1H),2.69–2.63(m,2H),2.34–2.27(m,5H),1.81–1.73(m,2H).

[0141] 产品D36:

[0142] 1-Bromo-3-(5-phenylpent-4-en-1-yl)benzene(D36)(C 17 H 17 Br)colorless oil;18.4mg,61%yield,E / Z=7.1:1, 1 H NMR(400MHz,Chloroform-d)major E isomer:δ7.37–7.32(m,4H),7.31–7.28(m,2H),7.23–7.19(m,1H),7.16(t,J=7.6Hz,1H),7.13–7.10(m,1H),6.40(d,J=15.8Hz,1H),6.25–6.18(m,1H),2.67–2.62(m,2H),2.28–2.22(m,2H),1.84–1.76(m,2H).

[0143] 产品D37:

[0144] 5-Phenylpent-4-en-1-ferrocene(D37) (C 21 H 22 Fe) yellow oil; 7.9 mg, 24% yield, E / Z = 9: 1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.36 (d, J = 7.0 Hz, 2H), 7.30 (t, J = 7.4 Hz, 2H), 7.22 - 7.18 (m, 1H), 6.40 (d, J = 15.8 Hz, 1H), 6.27 - 6.19 (m, 1H), 4.10 (s, 4H), 4.08 - 4.05 (m, 4H), 2.41 - 2.36 (m, 2H), 2.27 - 2.22 (m, 2H), 1.73 - 1.65 (m, 2H). Product D38:

[0145] 3-(6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-yl)propan-1-ferrocene(D38) (C 22 H 28 Fe) yellow oil; 11.1 mg, 32% yield, E / Z => 19: 1, 1 H NMR (400 MHz, Chloroform-d) δ 5.20 (dt, J = 3.0, 1.6 Hz, 1H), 4.09 (s, 5H), 4.06 - 3.98 (m, 4H), 2.39 - 2.16 (m, 5H), 2.10 - 2.06 (m, 1H), 2.05 - 1.90 (m, 3H), 1.57 (d, J = 7.4 Hz, 1H), 1.27 (s, 4H), 1.15 (d, J = 8.4 Hz, 1H), 0.85 (s, 3H).

[0146] Product D39:

[0147] 2-(2-Denzylidenecyclobutyl)ethan-1-ferrocene(D39) (C 23 H 24 Fe) yellow oil; 13.5 mg, 38% yield, E / Z => 19: 1, 1H NMR(400MHz,Chloroform-d)δ7.30(t,J=7.6Hz,2H),7.25–7.20(m,2H),7.18–7.13(m,1H),6.13(d,J=2.6Hz,1H),4.11(d,J=1.0Hz,4H),4.10–3.97(m,5H),3.21–3.06(m,1H),3.00–2.95(m,2H),2.41–2.31(m,2H),2.30–2.23(m,1H),1.98–1.89(m,1H),1.77–1.67(m,2H).

[0148] 产品D40: Tert-butyldimethyl({(8R,9S,13S,14S,17S)-13-methyl-3-[(E)-5-phenylpent-4-en-1-yl]-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl}oxy)silane(D40)

[0149] (C 35 H 50 OSi)white solid;27.3mg,53%yield,E / Z=7.1:1,melting point:55–59℃, 1 H NMR(400MHz,Chloroform-d)major E isomer:δ7.34–7.26(m,2H),7.26–7.16(m,2H),7.14–7.11(m,2H),6.93(s,1H),6.67(d,J=17.6Hz,1H),5.70(d,J=17.6Hz,1H),5.18(d,J=10.8Hz,1H),3.67–3.63(m,1H),2.88–2.85(m,2H),2.59(q,J=7.6Hz,1H),2.34–2.28(m,1H),2.26–2.19(m,1H),2.01–1.83(m,4H),1.70–1.62(m,1H),1.56–1.42(m,4H),1.42–1.27(m,4H),1.23–1.07(m,3H),0.90(s,9H),0.75(s,3H),0.05(s,3H),0.03(s,3H).

[0150] 产品D42: Hept-3-ene-1,7-diyldibenzene (D42) (C 19 H 22 ) colorless oil; 17.8 mg, 71% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.31 - 7.28 (m, 3H), 7.21 - 7.17 (m, 7H), 5.50 - 5.44 (m, 2H), 2.71 - 2.68 (m, 2H), 2.61 - 2.57 (m, 3H), 2.36 - 2.30 (m, 2H), 2.06 - 2.01 (m, 2H), 1.71 - 1.63 (m, 2H).

[0151] Product D43: Oct-4-en-1-ylbenzene (D43) (C 14 H 20 ) colorless oil; 11.3 mg, 60% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.30 - 7.26 (m, 2H), 7.20 - 7.16 (m, 3H), 5.44 - 5.39 (m, 2H), 2.63 - 2.59 (m, 2H), 2.05 - 2.00 (m, 2H), 1.99 - 1.94 (m, 2H), 1.72 - 1.65 (m, 2H), 1.40 - 1.35 (m, 2H), 0.88 (t, J = 3.4 Hz, 3H).

[0152] Product D44: Dodec-4-en-1-ylbenzene (D44) (C 18 H 28 ) colorless oil; 23.2 mg, 95% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.30 - 7.25 (m, 2H), 7.19 - 7.17 (m, 3H), 5.44 - 5.40 (m, 2H), 2.62 (d, J = 7.6 Hz, 2H), 2.04 - 2.01 (m, 2H), 2.00 - 1.96 (m, 2H), 1.72 - 1.65 (m, 2H), 1.38 - 1.28 (m, 10H), 0.89 (t, J = 2.0 Hz, 3H).

[0153] Product D45:

[0154] (4-Cyclohexylidenebutyl)benzene (D45) (C 16 H 22 ) colorless oil; 6.0 mg, 28% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.27 (d, J = 1.4 Hz, 2H), 7.18 (d, J = 7.4 Hz, 3H), 5.13 - 5.05 (m, 1H), 2.64 - 2.57 (m, 2H), 2.11 - 2.07 (m, 3H), 2.05 - 2.00 (m, 3H), 1.69 - 1.62 (m, 2H), 1.54 - 1.44 (m, 6H).

[0155] Product D46: Trimethyl(5-phenylpent-1-en-1-yl)silane (D46) (C 14 H 22 ) colorless oil; 12.2 mg, 69% yield, E / Z = 5:1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.30 - 7.27 (m, 2H), 7.20 - 7.18 (m, 3H), 6.08 - 6.00 (m, 1H), 5.65 (d, J = 18.6 Hz, 1H), 2.65 - 2.60 (m, 2H), 2.35 - 2.28 (m, 1H), 2.18 - 2.12 (m, 2H), 1.77 - 1.70 (m, 2H), 0.05 (s, 9H).

[0156] Product D48:

[0157] [3-(Cyclohex-1-en-1-yl)propyl]benzene (D48) (C 15 H 20 ) colorless oil; 12.6 mg, 63% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ

[0158] 7.31 - 7.25 (m, 2H), 7.19 (d, J = 7.4 Hz, 3H), 5.47 - 5.33 (m, 1H), 2.63 - 2.55 (m, 2H), 2.02 - 1.95 (m, 4H), 1.94 - 1.90 (m, 2H), 1.77 - 1.68 (m, 2H), 1.64 - 1.53 (m, 4H).

[0159] Product D49:

[0160] 6,6-Dimethyl-2-(3-phenylpropyl)bicyclo[3.1.1]hept-2-ene (D49) (C 18 H 24 ) colorless oil; 21.2 mg, 88% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.31 - 7.24 (m, 2H), 7.19 - 7.16 (m, 3H), 5.21 (t, J = 3.0 Hz, 1H), 2.60 (t, J = 7.8 Hz, 2H), 2.36 - 2.33 (m, 1H), 2.30 - 2.15 (m, 2H), 2.09 - 2.07 (m, 1H), 2.00 - 1.97 (m, 3H), 1.69 - 1.64 (m, 2H), 1.27 (s, 3H), 1.15 (d, J = 8.6 Hz, 1H), 0.84 (s, 3H).

[0161] Product D50:

[0162] 5-Isopropyl-2-(3-phenylpropyl)bicyclo[3.1.0]hex-2-ene (D50) (C 18 H 24 ) colorless oil; 20.4 mg, 85% yield, E / Z => 19:1, 1H NMR (400 MHz, Chloroform-d) δ 7.29 - 7.23 (m, 2H), 7.18 - 7.14 (m, 3H), 5.22 - 4.93 (m, 1H), 2.60 - 2.56 (m, 2H), 2.42 - 2.31 (m, 1H), 2.27 - 2.05 (m, 3H), 2.00 - 1.95 (m, 2H), 1.83 - 1.74 (m, 1H), 1.66 - 1.63 (m, 1H), 1.44 - 1.36 (m, 1H), 1.25 (s, 2H), 1.13 (d, J = 8.4 Hz, 1H), 0.93 (d, J = 6.8 Hz, 1H), 0.88 (d, J = 6.8 Hz, 1H), 0.82 (s, 2H).

[0163] Example 3: Preparation of polysubstituted olefin compounds C1-C10

[0164] The imidazoline-2-imine rare earth metal complex catalyst Sc-2 (16.6 mg, 0.01 mmol), triphenyl carbonium tetra(pentafluorophenyl)borate (18.4 mg, 0.01 mmol) were weighed into a bottle in the glove box, benzene (0.1 mL) and tetrahydrofuran (1.4 mg, 0.01 mmol) were added, activated at room temperature for 10 min, β-methyl styrene A (47.2 mg, 0.4 mmol) was added, and the glove box was taken out and reacted at 100 °C for 24 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain the product C, and the cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. The compounds C1-C9 were prepared according to the above method (the reaction conditions were the same, and the difference was that the specific raw materials were selected according to the structure of the compound).

[0165] The reaction formula structure is as follows:

[0166]

[0167] The imidazoline-2-imine rare earth metal complex catalyst Sc-2 (16.6 mg, 0.01 mmol), triphenyl carbonium tetra(pentafluorophenyl)borate (18.4 mg, 0.01 mmol) were weighed into a bottle in the glove box, benzene (0.1 mL) and tetrahydrofuran (1.4 mg, 0.01 mmol) were added, activated at room temperature for 10 min, β-methyl styrene A (47.2 mg, 0.4 mmol) was added, and the glove box was taken out and reacted at 100 °C for 24 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain the product C, and the cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. The compounds C1-C9 were prepared according to the above method (the reaction conditions were the same, and the difference was that the specific raw materials were selected according to the structure of the compound).

[0168] The reaction formula structure is as follows:

[0169]

[0170] The yield and E / Z ratio of each product are as follows:

[0171]

[0172] The important product characterization data are as follows:

[0173] Product C1 :

[0174] (4-Methylpent-1-ene-1,5-diyl)dibenzene (C1)

[0175] (C 18 H 20 ) colorless oil; 37.9 mg, 80% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.40 - 7.33 (m, 2H), 7.32 - 7.29 (m, 3H), 7.22 - 7.16 (m, 4H), 7.16 - 7.10 (m, 1H), 6.40 (d, J = 15.8 Hz, 1H), 6.24 (dt, J = 15.8, 7.2 Hz, 1H), 2.71 (dd, J = 13.2, 6.4 Hz, 1H), 2.46 (dd, J = 13.4, 8.0 Hz, 1H), 2.34 - 2.24 (m, 1H), 2.11 - 2.07 (m, 1H), 1.95 - 1.88 (m, 1H), 0.93 (d, J = 6.8 Hz, 3H).

[0176] Product C3:

[0177] 2,2'-(4-Methylpent-1-ene-1,5-diyl)bis(methylbenzene) (C3) (C 20 H 24 ) colorless oil; 27 mg, 51% yield, E / Z => 19:1, 1H NMR (400 MHz, Chloroform-d) δ 7.43 (d, J = 6.6 Hz, 1H), 7.19 - 7.12 (m, 7H), 6.62 (d, J = 15.6 Hz, 1H), 6.12 (dt, J = 15.2, 7.4 Hz, 1H), 2.76 (dd, J = 13.6, 6.2 Hz, 1H), 2.50 - 2.43 (m, 1H), 2.35 (d, J = 9.2 Hz, 7H), 2.22 - 2.14 (m, 1H), 1.97 - 1.89 (m, 1H), 0.98 (d, J = 6.8 Hz, 3H).

[0178] Product C4:

[0179] 4,4'-(4-Methylpent-1-ene-1,5-diyl)bis(isopropylbenzene) (C4) (C 24 H 32 ) colorless oil; 50.6 mg, 79% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.33 (d, J = 8.2 Hz, 2H), 7.23 - 7.17 (m, 4H), 7.13 (d, J = 8.2 Hz, 2H), 6.41 (d, J = 15.8 Hz, 1H), 6.22 (dt, J = 15.6, 7.2 Hz, 1H), 2.93 (p, J = 6.8 Hz, 2H), 2.70 (dd, J = 13.4, 6.4 Hz, 1H), 2.46 (dd, J = 13.4, 7.8 Hz, 1H), 2.34 - 2.27 (m, 1H), 2.15 - 2.06 (m, 1H), 1.94 (dt, J = 13.4, 6.8 Hz, 1H), 1.29 (dd, J = 7.0, 2.0 Hz, 12H), 0.96 (d, J = 6.8 Hz, 3H).

[0180] Product C7:

[0181] [(4-Methylpent-1-ene-1,5-diyl)bis(4,1-phenylene)]bis(methylsulfane) (C7)

[0182] (C 20 H 24 S2) colorless oil; 24.3 mg, 37% yield, E / Z => 19:1, 1H NMR (400 MHz, Chloroform-d) δ 7.27 - 7.24 (m, 2H), 7.19 (d, J = 7.8 Hz, 4H), 7.11 - 7.05 (m, 2H), 6.32 (d, J = 15.8 Hz, 1H), 6.16 (dt, J = 15.8, 7.2 Hz, 1H), 2.64 (dd, J = 13.6, 6.6 Hz, 1H), 2.47 (d, J = 1.4 Hz, 6H), 2.43 - 2.37 (m, 1H), 2.27 - 2.19 (m, 1H), 2.10 - 2.01 (m, 1H), 1.91 - 1.83 (m, 1H), 0.90 (d, J = 6.6 Hz, 3H).

[0183] Product C8:

[0184] 4,4'-(4-Methylpent-1-ene-1,5-diyl)bis(N,N-dimethylaniline) (C8) (C 22 H 30 N2) yellow oil; 20.4 mg, 31% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.24 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 8.6 Hz, 2H), 6.68 (dd, J = 8.6, 5.6 Hz, 4H), 6.28 (d, J = 15.8 Hz, 1H), 6.02 (dt, J = 15.8, 7.2 Hz, 1H), 2.92 (d, J = 8.8 Hz, 12H), 2.59 (dd, J = 13.6, 6.2 Hz, 1H), 2.33 (dd, J = 13.6, 7.8 Hz, 1H), 2.26 - 2.19 (m, 1H), 2.05 - 1.97 (m, 1H), 1.86 - 1.77 (m, 1H), 0.89 (d, J = 6.6 Hz, 3H).

[0185] Product C9:

[0186] (6-Methylnon-3-ene-1,9-diyl)dibenzene (C9)

[0187] (C 22 H 28 ) colorless oil; 15.8 mg, 27% yield, E / Z => 19:1, 1H NMR (400 MHz, Chloroform-d) δ 7.26 (d, J = 7.4 Hz, 5H), 7.17 (d, J = 6.8 Hz, 5H), 5.39 (q, J = 5.4 Hz, 2H), 2.65 (dd, J = 10.2, 5.4 Hz, 2H), 2.59 - 2.55 (m, 2H), 2.36 - 2.27 (m, 2H), 2.00 - 1.94 (m, 1H), 1.84 - 1.77 (m, 1H), 1.66 - 1.59 (m, 2H), 1.45 (q, J = 6.8 Hz, 1H), 1.35 - 1.30 (m, 1H), 1.17 - 1.11 (m, 1H), 0.82 (d, J = 6.6 Hz, 3H).

[0188] Product C10:

[0189] 4,4'-(4-Methylpent-1-ene-1,5-diyl)bis(fluorobenzene) (C10) (C 18 H 18 F2) colorless oil; 15.3 mg, 28% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ 7.32 - 7.26 (m, 2H), 7.13 - 7.09 (m, 2H), 7.01 - 6.95 (m, 4H), 6.34 (d, J = 15.8 Hz, 1H), 6.12 (dt, J = 15.4, 7.2 Hz, 1H), 2.66 (dd, J = 13.6, 6.4 Hz, 1H), 2.41 (dd, J = 13.6, 8.0 Hz, 1H), 2.30 - 2.18 (m, 1H), 2.09 - 2.02 (m, 1H), 1.91 - 1.83 (m, 1H), 0.91 (d, J = 6.6 Hz, 3H).

[0190] The advantageous effects of the present application are demonstrated by the following experimental examples.

[0191] Experimental Example 1: Screening test of different catalysts

[0192] The imidazoline-2-imine rare earth metal complex catalyst (0.01 mmol), triphenyl carbonium tetrakis(pentafluorophenyl)borate (9.2 mg, 0.01 mmol) were weighed into a bottle in a glove box, toluene (0.5 mL) was added, activated at room temperature for 10 min, β-methylstyrene A (35.4 mg, 0.3 mmol) and styrene B (10.4 mg, 0.1 mmol) were added, and the glove box was taken out to react at 100 ℃ for 12 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain product D, and the cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. Different catalysts were used in the experimental example, as shown in Table 1, and the single crystal structures of some catalysts are shown in Figs. 1 to 4

[0193] The reaction formula structure is as follows:

[0194]

[0195] Table 1. Product yield and E / Z ratio under different imidazoline-2-imine rare earth metal complex catalysts

[0196]

[0197] The above experimental results show that the product yield and E / Z comprehensive effect are best when Sc-2 is used.

[0198] Experimental Example 2: Screening test of different substrate ratios

[0199] The imidazoline-2-imine rare earth metal complex catalyst Sc-2 (8.3 mg, 0.01 mmol), triphenyl carbonium tetrakis(pentafluorophenyl)borate (9.2 mg, 0.01 mmol) were weighed into a bottle in a glove box, toluene (1.0 mL) was added, activated at room temperature for 5 min, β-methylstyrene A and styrene B (10.4 mg, 0.1 mmol) were added, and the glove box was taken out to react at 100 ℃ for 12 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain product D, and the cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. The reaction formula structure is as follows:

[0200] Table 2. Product yield and E / Z ratio under different substrate ratios

[0201] The above experimental results show that the product yield and E / Z comprehensive effect are best when reaction control A (0.3 mmol) and B (0.1 mmol) are reacted at 100 ℃ for 12 h in 1.0 mL of toluene.

[0202] ​In summary, the application provides a rare earth metal catalyst catalyzed allylic carbon hydrogen alkylation reaction by using imidazoline-2-imine, realizes synthesis of polysubstituted olefin compounds with high yield and high syn / anti ratio, and the method is simple, efficient, environment-friendly, good in substrate universality, and has wide application prospect.

Claims

1. A method for synthesizing polysubstituted olefin compounds by olefin coupling, characterized in that: The method comprises the following steps: reacting compound A0 with compound B0 under the action of an imidazoline-2-imine rare earth metal complex and an activator boron salt to obtain a polysubstituted olefin compound represented by formula I; in, R 1 、R 0 are independently selected from hydrogen, substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C4~C 10 Cycloalkyl, trimethylsilyl, substituted or unsubstituted C6~C 10 Aryl, wherein the substituent is selected from halogen, C1~C6 alkyl, C2~C 10 Alkenyl, C1~C6 alkylthio, C6~C 10 Aryl, phenoxy, C1~C6 alkyl substituted amino; Or, R 1 and R 0 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1~C6 alkyl; R 2 Selected from hydrogen, C1~C4 alkyl, C6~C 10 Aryl, Or, R 1 and R 2 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1~C6 alkyl; R 3 Selected from hydrogen, C1~C 10 Alkyl, C4~C 10 Cycloalkyl, C6~C 10 Aryl, Or, R 2 and R 3 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1~C6 alkyl; R 4 Selected from hydrogen, C1~C 10 alkyl; R 5 Selected from substituted or unsubstituted C6~C 10 Aryl, ferrocene, wherein the substituent is selected from halogen, C1~C6 alkyl, C2~C 10 Alkenyl, C1~C6 alkylthio, C6~C 10 Aryl, phenoxy, C1~C6 alkyl substituted amino, or two adjacent substituents connected to form a substituted or unsubstituted C4~C 20 Cycloalkyl, wherein the substituent is selected from C1~C6 alkyl, dimethyl tert-butylsilyl ether; The activator boron salt is selected from triphenylcarbon tetrakis (pentafluorophenyl) borate; The imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds: The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:10; The molar ratio of the compound B0 to the activator boron salt is 100:10; The molar ratio of compound B0 to compound A0 is 1:(1-10); The solvent of the reaction is one or a mixture of two or more of benzene and toluene; The reaction temperature is 100°C and the reaction time is 12-24 hours.

2. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1, characterized in that: The structural formula of the compound represented by Formula I is shown in any one of Formula II to Formula VI: Formula II Formula III Formula IV Formula V Formula VI.

3. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1 or 2, characterized in that: R 0 selected from hydrogen; R 1 Selected from hydrogen, substituted or unsubstituted C1~C7 alkyl, C6 cycloalkyl, trimethylsilyl, C6~C7 substituted or unsubstituted by 1~3 substituents 10 Aryl, wherein the substituent is selected from halogen, C1~C3 alkyl, C3 alkenyl, methylthio, phenyl, phenoxy, N,N -dimethylamino.

4. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1 or 2, characterized in that: R 2 Selected from hydrogen, phenyl; and / or, R 3 Selected from hydrogen, C1~C3 alkyl, phenyl; and / or, R 4 Selected from hydrogen and methyl.

5. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1 or 2, characterized in that: R 5 Selected from substituted or unsubstituted C6~C 10 Aryl, ferrocene, substituents selected from F, Br, C1~C4 alkyl, phenyl, methylthio, N,N -dimethylamino, or two adjacent substituents are connected to form a substituted or unsubstituted C 11 Cycloalkyl, wherein the substituent is selected from methyl and dimethyl tert-butylsilyl ether.

6. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1, characterized in that: R 1 and R 0 Connected to form a C6 cycloalkyl group; or, R 1 and R 2 connected to form a C6~C7 cycloalkyl group which is substituted or unsubstituted with 1~2 substituents, wherein the substituents are selected from C1~C3 alkyl groups; or, R 2 and R 3 Connected to form a C4 cycloalkyl group.

7. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1, characterized in that: The compound represented by formula I is selected from: 。 8. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1, characterized in that: The molar ratio of compound B0 to compound A0 is 1:3; The reaction time is 12 h.

9. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1, characterized in that: The imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds: 、 ; The activator boron salt is selected from triphenylcarbon tetrakis (pentafluorophenyl) borate; The solvent for the reaction is selected from toluene.

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