Method for synthesizing polysubstituted olefin compound through olefin coupling

Abstract

The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing a polysubstituted olefin compound through olefin coupling. The method comprises the following step: reacting a compound A0 with a compound B0 under the action of an imidazoline-2-imine rare earth metal complex and an activator boron salt to obtain the polysubstituted olefin compound as shown in the formula I. According to the synthesis method, a series of polysubstituted olefin compounds can be obtained at high yield and high cis-trans ratio, the method is simple, efficient and environment-friendly, the substrate is good in universality, and the application prospect is wide. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing multi-substituted olefin compounds by olefin coupling. Background Art

[0002] As a powerful strategy in organic synthetic chemistry and related fields, catalytic CH bond functionalization has received extensive attention in the past few decades. Developing new catalysts that are better or complementary to existing catalysts and providing 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 of double bonds (Z or E) in olefin molecules significantly affects the activity of bioactive molecules and the performance of materials. 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 precious metal palladium, which limits the substrate range, and the Wittig reaction has low atom economy. Therefore, the development of new methods for olefin synthesis has important theoretical significance and application prospects. 3 )-H bond activation to directly synthesize olefin derivatives has high step and atom economy and is in line with the concept of green chemistry development. 3 There are two main strategies for )-H functionalization reactions:

[0004] (1) Allyl carbon-hydrogen functionalization reaction catalyzed by precious metals (mainly Pd): This strategy uses the synergistic effect of precious metal Pd complexes and external oxidants to activate the allylic CH bond of terminal olefins to form an electrophilic π-allylpalladium intermediate, which then couples with a nucleophilic reagent. White and Gong reported different catalytic systems to achieve the above-mentioned transformation (J.Am.Chem.Soc.2008,130,14090-14091, Acc.Chem.Res.2020,53,2841-2854.).

[0005]

[0006] (2) Allyl C-H functionalization reaction catalyzed by cheap metals (mainly alkali metals and Fe, etc.): This strategy uses the weak interaction between metals and double bonds to activate the allylic CH bonds of olefins to form nucleophilic allylic cheap metal species, which then couple with electrophilic reagents to generate the corresponding olefin derivatives. In 2023, Wang's research group reported the allylic CH functionalization of propylene and simple olefins catalyzed by cationic cyclopentadienyl dicarbonyl iron complexes. The base pulls out the proton at the allylic position to generate a nucleophilic allylic metal species, which then undergoes an addition reaction on the aldehyde (Angew. Chem. Iht. Ed. 2023, 62, e202216309.). Alkali metals can catalyze the activation of allylic carbon-hydrogen bonds through acid-base reactions due to their strong alkalinity (J. Am. Chem. Soc. 2017, 139, 4362-4365.).

[0007]

[0008] Although the allylic C (sp 3 Although the above-mentioned important progress has been made in the functionalization reaction of )-H, 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 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 been investigated. Org. Lett. 2018, 20, 71 77-71 8).

[0009] Rare earth metals are a general term for 17 elements including scandium, yttrium and lanthanides (La-Lu). Rare earth metals have unique electronic structures and chemical properties different from main group metals and post-transition metals. Thanks to the strong heteroatom affinity of rare earth metals and their ability to rapidly migrate and insert into unsaturated double bonds, rare earth organic complexes have been successfully used in direct carbon-hydrogen functionalization reactions of heteroatom-containing substrates (such as pyridine, sulfide, amine, imine, etc.) with alkenes and alkynes (Tetrahedron 2023, 135, 133323-133339). In addition to the interactions between rare earth heteroatoms, rare earth metals also have weak interactions with alkenes or aromatics. These weak interactions play an important role in the activity and selectivity control of heteroatom substrate hydrogen functionalization reactions and olefin polymerization reactions.

[0010] 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 reaction (Chem. Sci. 2023, 14, 31 32-3139, Sci. China Chem. 2023, 66, 1804-1813, Chem. Eur. J. 2024, e202401014).

[0011] Nevertheless, utilizing rare earth metal-π interactions to achieve allylic or benzylic C-H bond activation has not been discovered or reported. Summary of the invention

[0012] The object of the present invention is to provide a process for the cross-coupling and dimerization of olefins.

[0013] A method for synthesizing a polysubstituted olefin compound by olefin coupling, comprising the following steps: a compound A0 and a compound B0 react under the action of an imidazoline-2-imine rare earth metal complex and an activator boron salt to obtain a polysubstituted olefin compound of formula I;

[0014]

[0015] in,

[0016] 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 10alkenyl, C1-C6 alkylthio, C6-C 10 Aryl, phenoxy, C1-C6 alkyl substituted amino;

[0017] Or, R 1 and R 0 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1 to C6 alkyl;

[0018] R 2 Selected from hydrogen, C1-C4 alkyl, C6-C 10 Aryl,

[0019] Or, R 1 and R 2 Connect to form substituted or unsubstituted C3~C 10 Cycloalkyl, wherein the substituent is selected from C1 to C6 alkyl;

[0020] R 3 Selected from hydrogen, C1~C 10 Alkyl, C4~C 10 Cycloalkyl, C6~C 10 Aryl,

[0021] 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;

[0022] R 4 Selected from hydrogen, C1~C 10 alkyl;

[0023] 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-butyl silyl ether.

[0024] Preferably, the structural formula of the compound represented by Formula I is as shown in any one of Formula II to Formula VI:

[0025]

[0026]

[0027] Preferably, R0 Selected from hydrogen;

[0028] R 1 is selected from hydrogen, substituted or unsubstituted C1-C7 alkyl, C6 cycloalkyl, trimethylsilyl, C b ~C 10 Aryl, wherein the substituent is selected from halogen, C1-C3 alkyl, C3 alkenyl, methylthio, phenyl, phenoxy, N,N-dimethylamino.

[0029] Preferably, R 2 is selected from hydrogen, phenyl;

[0030] and / or, R 3 Selected from hydrogen, C1-C3 alkyl, phenyl;

[0031] and / or, R 4 Selected from hydrogen and methyl.

[0032] Preferably, R 5 Selected from substituted or unsubstituted ethyl, substituted or unsubstituted C6~C 10 Aryl, ferrocene, the substituent is 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.

[0033] Preferably, R 1 and R 0 Connected to form a C6 cycloalkyl group;

[0034] 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;

[0035] or, R 2 and R 3 Connected to form a C4 cycloalkyl group.

[0036] Preferably, the compound represented by formula I is selected from:

[0037]

[0038]

[0039]

[0040]

[0041] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0042]

[0043] wherein M is selected from Sc, Y;

[0044] m and n are independently taken from 1, 2, 3, 4, and 5, respectively;

[0045] R 6 Selected from C1-C6 alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl, substituted or unsubstituted C6~C 10 Aryl, wherein the substituent is C1-C6 alkyl, C6-C 10 Aryl;

[0046] The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:(2-10);

[0047] The molar ratio of the compound B0 to the activator boron salt is 100:(2-10);

[0048] The molar ratio of the compound B0 to the compound A0 is 1:(0.5-100);

[0049] The solvent of the reaction is an organic solvent;

[0050] The reaction temperature is 10-120°C and the reaction time is 12-24h.

[0051] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0052]

[0053]

[0054] The activator boron salt is selected from triphenylcarbon tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)borane, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate;

[0055] The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:10;

[0056] The molar ratio of the compound B0 to the activator boron salt is 100:10;

[0057] The molar ratio of the compound B0 to the compound A0 is 1:3;

[0058] The solvent of the reaction is one or a mixture of two or more of halogenated hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and aliphatic hydrocarbons, preferably one or a mixture of two or more of methanol, dichloromethane, n-hexane, ethyl ether, o-xylene, m-xylene, p-xylene, mesitylene, trifluorotoluene, chlorobenzene, benzene, and toluene;

[0059] The reaction temperature in step (1) is 100° C. and the reaction time is 12 h.

[0060] Preferably, the imidazoline-2-imine rare earth metal complex catalyst is selected from at least one of the following compounds:

[0061] The activator boron salt is selected from triphenylcarbon tetrakis(pentafluorophenyl)borate;

[0062] The solvent for the reaction is selected from toluene.

[0063] Definitions of terms used in the present invention: Unless otherwise stated, the initial definitions provided for groups or terms in this document apply to the groups or terms throughout the specification; for terms that are not specifically defined in this document, the meaning that a person skilled in the art can give them should be given based on the disclosure and context.

[0064] "Substitution" means that the hydrogen atoms in a molecule are replaced by other different atoms or molecules. "Substitution" can mean substitution by one group or by at least two groups.

[0065] The minimum and maximum carbon atom content in a hydrocarbon group is indicated by a prefix, for example, the prefix C a -C b Alkyl refers to any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, "C1-C4 alkyl" refers to an alkyl group containing from 1 to 4 carbon atoms.

[0066] "Alkyl" refers to a saturated hydrocarbon chain with a specified number of member atoms. For example, C1-C6 alkyl refers to an alkyl group with 1 to 6 member atoms, such as 1 to 4 member atoms. The alkyl group can be straight or branched. Representative branched alkyl groups have one, two or three branches. The alkyl group may 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 tert-butyl), pentyl (n-pentyl, isopentyl and neopentyl) and hexyl. The alkyl group may also be a part of other groups, such as C1-C6 alkoxy.

[0067] "Cycloalkyl" refers to a saturated or partially saturated cyclic group having 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 polycyclic systems with aromatic and non-aromatic rings without ring heteroatoms, the term "cycloalkyl" (e.g., 5,6,7,8,-tetrahydronaphthalene-5-yl) is applicable when the point of attachment is located at a non-aromatic carbon atom. The term "cycloalkyl" includes cycloalkenyl groups such as cyclohexenyl. Examples of cycloalkyl groups include, for example, adamantyl, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclooctyl, cyclopentenyl and cyclohexenyl. Examples of cycloalkyl groups including polybicycloalkyl ring systems are bicyclohexyl, bicyclopentyl, bicyclooctyl, etc. Two such bicycloalkyl polycyclic structures are exemplified and named below: Biscyclohexyl and Biscyclohexyl.

[0068] "Alkenyl" refers to a straight or branched chain hydrocarbon group having 2 to 10 carbon atoms, and in some embodiments 2 to 6 carbon atoms or 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 a to b carbon atoms and is meant to include, for example, ethenyl, propenyl, isopropenyl, 1,3-butadienyl, and the like.

[0069] "Halogen" is fluorine, chlorine, bromine or iodine.

[0070] “R a and R b 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, so that R a and R b The atoms or chains of atoms that are connected together as part of the ring structure are related to R a and R b Together they form a ring.

[0071] "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.

[0072] The hydrogen atoms in the compounds of the present invention may be various isotopes of hydrogen, such as protium ( 1 H), deuterium ( 2 H) or tritium ( 3 H).

[0073] 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, iBu is isobutyl, Ad is adamantyl, Cy is cyclohexyl, OTBS is dimethyl tert-butylsilyl, and TMS is trimethylsilyl.

[0074] The present invention provides a new method for efficiently catalyzing the cross-coupling and dimerization of olefins using a rare earth organic complex, and synthesizes a series of olefin derivatives with high selectivity. Compared with the prior art, the present invention has the following beneficial effects:

[0075] 1. Develop a new type of imidazoline-2-imine rare earth metal complex catalyst for the hydrocarbon alkylation reaction of β-methylstyrene and toluene substrates, achieving high yield and high cis-trans selectivity to synthesize multi-substituted olefins and their analogs, with good substrate universality;

[0076] 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.

[0077] 3. The product is easy to separate from the catalyst and raw materials; the reaction system is simple and clean, which conforms to the atomic economy of green chemistry;

[0078] The invention utilizes imidazoline-2-imine rare earth metal catalyst to catalyze allylic hydrocarbon alkylation reaction, thereby realizing 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.

[0079] Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

[0080] The above contents of the present invention are further described in detail below through specific implementation methods in the form of embodiments. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 : Single crystal structure of catalyst Sc-2.

[0082] Figure 2 : Single crystal structure of catalyst Sc-4.

[0083] Figure 3 : Single crystal structure of catalyst Sc-11.

[0084] Figure 4 : Single crystal structure of catalyst Sc-13. DETAILED DESCRIPTION

[0085] The raw materials and equipment used in the present invention are all known products, which are obtained by purchasing commercial products. The reaction operations and product treatments involved in the examples are all carried out in anhydrous and oxygen-free Schlenk tube technology and an argon glove box. The solvents and reagents used are all treated with anhydrous and oxygen-free treatment.

[0086] Example 1: Catalyst Synthesis

[0087]

[0088] Step 1: In a glove box, Sc(CH2C6H4NMe2-o)3 (0.5 mmol, 1.0 equivalent) and imidazoline-2-imide (0.5 mmol, 1.0 equivalent) were dissolved in tetrahydrofuran, and 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. The mixture was cooled to room temperature and a large amount of product was precipitated. The mixture was filtered, and the solid was washed with n-hexane and dried under vacuum to obtain catalysts Sc-1-Sc-12. Characterization data of representative catalysts are as follows:

[0089]

[0090] Sc-2(C 53 H 76 N5Sc) Synthesis method see step 1. (white solid, 311.0 mg, 75% yield). 1 H NMR (400MHz, Benzene-d6) δ7.19 (s, 2H), 7.09 (s, 2H), 7.05-6.97 (m, 4H), 6.83-6.81 (m, 2H), 6.75 (d, J=8.0Hz, 2H), 3.41 (s, 2H), 2.99-2.77 (m, 4H) , 2.33 (s, 6H), 1.97 (s, 6H), 1.63 (d, J = 5.8Hz, 8H), 1.47 (s, 6H), 1.35 (s, 2 H), 1.30 (d, J=7.0Hz, 12H), 1.22 (d, J=6.8Hz, 12H), 1.01 (d, J=6.6Hz, 6H).

[0091]

[0092] Sc-4(C 67 H 92 N5Sc) Synthesis method see step 1. (white solid, 354.0 mg, 70% yield). 1H NMR (400MHz, Benzene-d6) δ7.43 (s, 2H), 7.35 (d, J=7.8Hz, 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=10.8Hz, 2H), 1.33-1.16 (m, 18H), 1.08 (d, J=6.8Hz, 6H).

[0093]

[0094] Sc-11(C 91 H 88 N5Sc) Synthesis method see step 1. (white solid, 310.0 mg, 50% yield). 1 H NMR (400MHz, Benzene-d6) δ7.89 (d, J=7.6Hz, 3H), 7.82-7.74 (m, 3H), 7.49 (t, J=7.6Hz, 3H), 7.40 -7.31 (m, 4H), 7.16 (s, 13H), 7.03 (t, J=4.0Hz, 10H), 6.98 (t, J=6.8Hz, 3H), 6.89-6.84 (m, 6H), 6.7 8-6.73 (m, 4H), 6.68-6.55 (m, 5H), 5.88 (s, 2H), 4.56 (s, 2H), 2.60 (p, J=6.8Hz, 2H), 2.38 (s, 6H), 2.23 (d, J=10.4Hz, 2H), 1.96 (d, J=10.2Hz, 2H), 1.66 (s, 6H), 1.36 (s, 2H), 1.04 (d, J=6.8Hz, 10H).

[0095]

[0096] Step 2: In a glove box, ScCl3·(THF)3 (0.5 mmol, 1.0 equiv) and LiCH2SiMe3 (0.5 mmol, 1.0 equiv) were dissolved in tetrahydrofuran, stirred at room temperature for 2 hours, and a tetrahydrofuran solution of imidazoline-2-imide was added. The reaction mixture was allowed to react for 12 hours at room temperature, the solvent was removed under vacuum, the solid was dissolved in n-hexane, filtered, and the filtrate was concentrated. The solid was recrystallized from THF / pentane (1:2, v / v) at -30°C to obtain colorless crystals. The yield was 40%.

[0097] The solid was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of C3H5MgCl (2 equiv) was added. The reaction was carried out at room temperature for 12 hours. The solvent was removed under vacuum, and the solid was dissolved in n-hexane. The mixture was filtered and the filtrate was concentrated. The solid was recrystallized from THF / pentane (1:2, v / v) at -30°C to obtain colorless crystals of Sc-13. The solid was filtered and washed with n-hexane and dried under vacuum. The yield was 50%.

[0098] 1 H NMR (400MHz, Benzene-d6) δ7.22-7.13(m, 2H), 7.14(d, J=6.6Hz, 4H), 6.62-6.38(m, 2H), 3.34(q, J=6.8Hz, 4H), 3.12(d , J=6.4Hz, 4H), 2.85 (d, J=12.2Hz, 8H), 1.56 (s, 6H), 1.48 (d, J=6.8Hz, 12H), 1.22 (d, J=7.0Hz, 12H), 1.13-1.08 (m, 4H).

[0099]

[0100] Step 3: In a glove box, Sc(CH2TMS)3·2THF (0.5mmol, 1.0equiv) and imidazoline-2-imide (0.5mmol, 1.0equiv) were dissolved in tetrahydrofuran, reacted at room temperature for 12 hours, the solvent was removed under vacuum, the solid was dissolved in n-hexane, filtered, concentrated, recrystallized at -30°C to obtain colorless crystals, filtered, and dried to obtain catalysts Sc-15-Sc-17. Representative catalyst characterization data are as follows:

[0101]

[0102] Sc-15(C 47 H 82 N3OScSi2) Synthesis method see step 3. (white crystal, 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, 1 6H), 0.61 (t, J=7.4Hz, 12H), 0.00 (s, 18H), -0.56 (s, 4H).

[0103] Example 2: Preparation of polysubstituted olefin compounds D1-D50

[0104] 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, 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 and reacted at 100 ° C for 12 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain product D, and the product cis-trans ratio was determined by using a nuclear magnetic resonance spectrometer. The reaction structure is as follows:

[0105]

[0106] 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:

[0107]

[0108]

[0109]

[0110] Important product characterization data are as follows:

[0111] Product D1:

[0112] 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)major Eisomer: 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 ) colorless oil; 26.2 mg, 99% yield, E / Z = 9:1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.28 (d, J = 1.6 Hz, 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 = 6.8 Hz, 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, 11H 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, 1 1H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.34 - 7.26 (m, 6H), 7.21 - 7.17 (m, 3H), 7.09 (d, J = 7.6 Hz, 1H), 7.01 - 6.97 (m, 2H), 6.95 - 6.92 (m, 2H), 6.36 (d, J = 15.8 Hz, 1H), 6.16 - 6.12 (m, 1H), 2.68 - 2.64 (m, 2H), 2.27 - 2.19 (m, 2H), 1.82 - 1.76 (m, 2H).

[0120] Product D10:

[0121] 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 1H NMR (400 MHz, Chloroform-d) δ 7.32 - 7.26 (m, 4H), 7.2l - 7.18 (m, 5H), 6.35 (d, J = 15.8, 1H), 6.24 - 6.17 (m, 1H), 2.72 - 2.63 (m, 2H), 2.48 (s, 3H), 2.31 - 2.19 (m, 2H), 1.85 - 1.79 (m, 2H).

[0122] Product D11:

[0123] 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, 5H), 7.24 - 7.19 (m, 4H), 6.71 (d, J = 8.8 Hz, 2H), 6.37 - 6.32 (d, J = 15.8 Hz, 1H), 6.10 - 6.02 (m, 1H), 2.97 (s, 6H), 2.71 - 2.67 (m, 2H), 2.28 - 2.22 (m, 2H), 1.86 - 1.77 (m, 2H.

[0124] Product D12:

[0125] 1 - Fluoro - 4 - (5 - phenylpent - 1 - en - 1 - yl)benzene (D12) (C 17 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).

[0126] Product D14:

[0127] 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, 11H 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).

[0128] Product D19:

[0129] 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 1H NMR (400 MHz, Chloroform-d) δ 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).

[0130] Product D20:

[0131] (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 1H 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).

[0132] Product D22:

[0133] (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: δ7.39 (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).

[0134] Product D26:

[0135] Dec-4-en-1-ylbenzene(D26)(C 16 H 24 ) colorless oil; 7.6 mg, 35% yield, E / Z => 19:1, 1 H NMR (400 MHz, 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 = 7.2 Hz, 3H).

[0136] Product D27:

[0137] (5-Cyclohexylpent-4-en-1-yl)benzene(D27)(C 17 H 24 ) colorless oil; 10.5 mg, 46% yield, E / Z => 19:1, 11H NMR (400 MHz, Chloroform-d) δ 7.30 - 7.26 (m, 2H), 7.20 - 7.15 (m, 3H), 5.37 (q, J = 2.6 Hz, 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 = 5.6 Hz, 4H), 1.09 - 0.99 (m, 2H).

[0138] Product D28:

[0139] Hex-2-ene-1,6-diyldibenzene (D28) (C 19 H 22 ) colorless oil; 13.0 mg, 52% yield, E / Z => 19:1, 1 1H NMR (400 MHz, Chloroform-d) δ 7.37 (d, J = 7.2 Hz, 1H), 7.32 - 7.25 (m, 6H), 7.23 - 7.14 (m, 8H), 6.38 (d, J = 15.8 Hz, 1H), 6.13 (dd, J = 15.8, 8.0 Hz, 1H), 5.64 - 5.47 (m, 2H), 3.34 (d, J = 6.2 Hz, 2H), 2.71 - 2.57 (m, 3H), 2.38 - 2.31 (m, 1H), 2.07 (q, J = 7.0 Hz, 2H), 1.75 - 1.67 (m, 3H), 1.12 (d, J = 6.8 Hz, 2H).

[0140] Product D29:

[0141] [2-(2-Benzylidenecyclobutyl)ethyl]benzene (D29) (C 19 H 20 ) colorless oil; 24.6 mg, 99% yield, E / Z = 4:1, 11H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.27 - 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).

[0142] Product D30:

[0143] (2-Methylpent-1-ene-1,5-diyl)dibenzene (D30) (C 18 H 20 ) colorless oil; 14.4 mg, 62% yield, E / Z = 4:1, 1 1H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.26 (t, J = 7.4 Hz, 5H), 7.17 - 7.11 (m, 5H), 6.29 (s, 1H), 2.66 (t, J = 7.8 Hz, 1H), 2.60 (t, J = 7.8 Hz, 2H), 2.28 (dd, J = 9.6, 6.4 Hz, 2H), 1.88 (s, 3H), 1.82 (t, J = 7.8 Hz, 2H).

[0144] Product D31:

[0145] 1-Methyl-2-(5-phenylpent-4-en-1-yl)benzene (D31) (C 18 H 20 ) colorless oil; 14.2 mg, 60% yield, E / Z = 4.4:1, 1 1H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.37 - 7.33 (m, 2H), 7.23 - 7.18 (m, 2H), 7.15 - 7.10 (m, 5H), 6.42 (d, J = 15.8 Hz, 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).

[0146] Product D36:

[0147] 1-Bromo-3-(5-phenylpent-4-en-1-yl)benzene (D36) (C 17 H 17 Br) colorless oil; 18.4 mg, 61% yield, E / Z = 7.1:1, 1 H NMR (400 MHz, 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 = 7.6 Hz, 1H), 7.13 - 7.10 (m, 1H), 6.40 (d, J = 15.8 Hz, 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).

[0148] Product D37:

[0149] 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: δ7.36 (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).

[0150] Product D38:

[0151] 3-(6,6-Dimethylbicycl0[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 1H 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).

[0152] Product D39:

[0153] 2-(2-Denzylidenecyclobutyl)ethan-1-ferrocene (D39) (C 23 H 24 Fe) yellow oil; 13.5 mg, 38% yield, E / Z => 19:1, 1 1H NMR (400 MHz, Chloroform-d) δ 7.30 (t, J = 7.6 Hz, 2H), 7.25 - 7.20 (m, 2H), 7.18 - 7.13 (m, 1H), 6.13 (d, J = 2.6 Hz, 1H), 4.11 (d, J = 1.0 Hz, 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).

[0154] Product D40:

[0155] 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)

[0156] (C 35 H 50 OSi) white solid; 27.3 mg, 53% yield, E / Z = 7.1:1, melting point: 55 - 59 °C, 11H NMR (400 MHz, Chloroform-d) major E isomer: δ 7.34 - 7.26 (m, 2H), 7.26 - 7.16 (m, 2H), 7.14 - 7.11 (m, 2H), 6.93 (s, 1H), 6.67 (d, J = 17.6 Hz, 1H), 5.70 (d, J = 17.6 Hz, 1H), 5.18 (d, J = 10.8 Hz, 1H), 3.67 - 3.63 (m, 1H), 2.88 - 2.85 (m, 2H), 2.59 (q, J = 7.6 Hz, 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).

[0157] Product D42:

[0158] Hept-3-ene-1,7-diyldibenzene (D42) (C 19 H 22 ) colorless oil; 17.8 mg, 71% yield, E / Z => 19:1, 1 1H 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).

[0159] Product D43:

[0160] Oct-4-en-1-ylbenzene (D43) (C 14 H 20 ) colorless oil; 11.3 mg, 60% yield, E / Z => 19:1, 11H 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).

[0161] Product D44:

[0162] Dodec-4-en-1-ylbenzene (D44) (C 18 H 28 ) colorless oil; 23.2 mg, 95% yield, E / Z => 19:1, 1 1H 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).

[0163] Product D45:

[0164] (4-Cyclohexylidenebutyl)benzene (D45) (C 16 H 22 ) colorless oil; 6.0 mg, 28% yield, E / Z => 19:1, 1 1H 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).

[0165] Product D46:

[0166] Trimethyl(5-phenylpent-1-en-1-yl)silane (D46) (C14 H 22 Si) colorless oil; 12.2 mg, 69% yield, E / Z = 5:1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ7.30 - 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).

[0167] Product D48:

[0168] [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) δ7.31 - 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).

[0169] Product D49:

[0170] 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, 1H NMR (400MHz, Chloroform-d) δ7.31-7.24 (m, 2H), 7.19-7.16 (m, 3H), 5.21 (t, J=3.0Hz, 1H), 2.60 (t, J=7.8Hz, 2H), 2.36-2.33 (m, 1 H), 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=8.6Hz, 1H), 0.84(s, 3H).

[0171] Product D50:

[0172] 5-Isopropyl-2-(3-phenylpropyl)bicyclo[3.1.0]hex-2-ene(D50)(C 18 H 24 )colorless oil; 20.4mg, 85% yield, E / Z=>19:1, 1 H NMR (400MHz, Chloroform-d) δ7.29-7.23 (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=8.4Hz, 1H), 0.93 (d, J=6.8Hz, 1H), 0.88 (d, J=6.8Hz, 1H), 0.82 (s, 2H).

[0173] Example 3: Preparation of polysubstituted olefin compounds C1-C10

[0174] In a glove box, imidazoline-2-imine rare earth metal complex catalyst Sc-2 (16.6 mg, 0.01 mmol) and triphenylcarbon tetrakis (pentafluorophenyl) borate (18.4 mg, 0.01 mmol) were weighed into a bottle, benzene (0.1 mL) and tetrahydrofuran (1.4 mg, 0.01 mmol) were added, activated at room temperature for 10 min, β-methylstyrene 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 product C, and the cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. The structures of compounds C1-C9 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).

[0175] The reaction structure is as follows:

[0176]

[0177] In a glove box, imidazoline-2-imine rare earth metal complex catalyst Sc-15 (16.2 mg, 0.01 mmol) and triphenyl carbon tetrakis (pentafluorophenyl) borate (18.4 mg, 0.01 mmol) were weighed into a bottle, benzene (0.1 mL) was added, activated at room temperature for 10 min, allylbenzene B (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, and the product C10 was eluted with petroleum ether. The cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. The structures of compounds C1, C3, and C10 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).

[0178] The reaction structure is as follows:

[0179]

[0180] The yield and cis-trans ratio of each product are as follows:

[0181]

[0182]

[0183] Important product characterization data are as follows:

[0184] Product C1:

[0185] (4-Methylpent-1-ene-1,5-diyl)dibenzene(C1)

[0186] (C 18 H20 ) colorless oil;37.9 mg, 80% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) major E isomer: δ7.40 - 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).

[0187] Product C3:

[0188] 2,2′-(4-Methylpent-1-ene-1,5-diyl)bis(methylbenzene) (C3)

[0189] (C 20 H 24 ) colorless oil;27 mg, 51% yield, E / Z => 19:1, 1 H NMR (400 MHz, Chloroform-d) δ7.43 (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).

[0190] Product C4:

[0191] 4,4′-(4-Methylpent-1-ene-1,5-diyl)bis(isopropylbenzene) (C4)

[0192] (C 24 H 32)colorless oil;50.6mg,79%yield,E / Z=>19∶1, 1 H NMR(400MHz,Chloroform-d)δ7.33(d,J=8.2Hz,2H),7.23 - 7.17(m,4H),7.13(d,J=8.2Hz,2H),6.41(d,J=15.8Hz,1H),6.22(dt,J=15.6,7.2Hz,1H),2.93(p,J=6.8Hz,2H),2.70(dd,J=13.4,6.4Hz,1H),2.46(dd,J=13.4,7.8Hz,1H),2.34 - 2.27(m,1H),2.15 - 2.06(m,1H),1.94(dt,J=13.4,6.8Hz,1H),1.29(dd,J=7.0,2.0Hz,12H),0.96(d,J=6.8Hz,3H).

[0193] Product C7:

[0194] [(4 - Methylpent - 1 - ene - 1,5 - diyl)bis(4,1 - phenylene)]bis(methylsulgane)(C7)

[0195] (C 20 H 24 S2)colorless oil;24.3mg,37%yield,E / Z=>19∶1, 1 H NMR(400MHz,Chloroform - d)δ7.27 - 7.24(m,2H),7.19(d,J=7.8Hz,4H),7.11 - 7.05(m,2H),6.32(d,J=15.8Hz,1H),6.16(dt,J=15.8,7.2Hz,1H),2.64(dd,J=13.6,6.6Hz,1H),2.47(d,J=1.4Hz,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=6.6Hz,3H).

[0196] Product C8:

[0197] 4,4′-(4 - Methylpent - 1 - ene - 1,5 - diyl)bis(N,N - dimethylaniline)(C8)

[0198] (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).

[0199] Product C9:

[0200] (6-Methylnon-3-ene-1,9-diyl)dibenzene (C9)

[0201] (C 22 H 28 ) colorless oil; 15.8 mg, 27% yield, E / Z => 19:1, 1 H 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).

[0202] Product C10:

[0203] 4,4′-(4-Methylpent-1-ene-1,5-diyl)bis(fluorobenzene) (C10)

[0204] (C18 H 18 F2) colorless oil; 15.3mg, 28% yield, E / Z=>19:1, 1 H NMR (400MHz, Chloroform-d) δ7.32-7.26 (m, 2H), 7.13-7.09 (m, 2H), 7.01-6.95 (m, 4H), 6.34 (d, J=15.8Hz, 1H), 6.12 (dt, J=1 5.4, ​​7.2Hz, 1H), 2.66 (dd, J=13.6, 6.4Hz, 1H), 2.41 (dd, J=13.6, 8.0Hz, 1H), 2 .30-2.18(m, 1H), 2.09-2.02(m, 1H), 1.91-1.83(m, 1H), 0.91(d, J=6.6Hz, 3H).

[0205] The beneficial effects of the present invention are demonstrated by experimental examples below.

[0206] Experimental Example 1: Screening test of different catalysts

[0207] In a glove box, imidazoline-2-imine rare earth metal complex catalyst (0.01mmol) and triphenylcarbon tetrakis (pentafluorophenyl) borate (9.2mg, 0.01mmol) were weighed into a bottle, toluene (0.5mL) was added, activated at room temperature for 10min, β-methylstyrene A (35.4mg, 0.3mmol) and styrene B (10.4mg, 0.1mmol) were added, and the glove box was taken out to react at 100°C for 12h. The reaction solution was directly purified by silica gel column chromatography, and product D was eluted with petroleum ether. The cis-trans ratio of the product was determined by using a nuclear magnetic resonance spectrometer. Different catalysts were used in this experimental example, as shown in Table 1. The single crystal structures of some catalysts are shown in Table 1. Figures 1 to 4 shown.

[0208] The reaction structure is as follows:

[0209]

[0210] Table 1. Product yields and cis-trans ratios of different imidazoline-2-imine rare earth metal complexes

[0211]

[0212]

[0213] The above experimental results show that the comprehensive effect of product yield and E / Z is best when Sc-2 is used.

[0214] Experimental Example 2: Screening test with different substrate ratios

[0215] 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, 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 and reacted at 100 ° C for 12 h. The reaction solution was directly purified by silica gel column chromatography, eluted with petroleum ether to obtain product D, and the product cis-trans ratio was determined by using a nuclear magnetic resonance spectrometer. The reaction structure is as follows:

[0216] Table 2. Product yield and cis-trans ratio at different substrate ratios

[0217]

[0218] The above experimental results show that the product yield and E / Z comprehensive effect are best when reaction A (0.3 mmol) and B (0.1 mmol) are reacted in 1.0 mL of toluene at 100°C for 12 h.

[0219] In summary, the present invention provides a method for catalyzing the allylic hydrocarbon alkylation reaction using imidazoline-2-imine rare earth metal catalyst, 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.

Claims

1. A method for synthesizing polysubstituted olefin compounds by olefin coupling, characterized in that: The method comprises the following steps: a compound A0 reacts with a compound B0 under the action of an imidazoline-2-imine rare earth metal complex and an activator boron salt to obtain a multi-substituted 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 to 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 to 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 to 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 and dimethyl tert-butyl silyl ether.

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:

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 is 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.

4. The method for synthesizing polysubstituted olefin compounds by olefin coupling according to claim 1 or 2, characterized in that: R 2 is 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 ethyl, substituted or unsubstituted C6~C 10 Aryl, ferrocene, the substituent is 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 multi-substituted 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 multi-substituted olefin compounds by olefin coupling according to claim 1, characterized in that: The compound shown in formula I is selected from:

8. The method for synthesizing multi-substituted 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: wherein M is selected from Sc, Y; m and n are independently taken from 1, 2, 3, 4, and 5, respectively; R 6 Selected from C1-C6 alkyl, substituted or unsubstituted C4-C 10 Cycloalkyl, substituted or unsubstituted C6~C 10 Aryl, wherein the substituent is C1-C6 alkyl, C6-C 10 Aryl; The molar ratio of the compound B0 to the imidazoline-2-imine rare earth metal catalyst is 100:(2-10); The molar ratio of the compound B0 to the activator boron salt is 100:(2-10); The molar ratio of the compound B0 to the compound A0 is 1:(0.5-100); The solvent of the reaction is an organic solvent; The reaction temperature is 10-120°C and the reaction time is 12-24h.

9. The method for synthesizing multi-substituted olefin compounds by olefin coupling according to claim 8, 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, tris(pentafluorophenyl)borane, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate; 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 the compound B0 to the compound A0 is 1:3; The solvent of the reaction is one or a mixture of two or more of halogenated hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and aliphatic hydrocarbons, preferably one or a mixture of two or more of methanol, dichloromethane, n-hexane, ethyl ether, o-xylene, m-xylene, p-xylene, mesitylene, trifluorotoluene, chlorobenzene, benzene, and toluene; The reaction temperature in step (1) is 100° C. and the reaction time is 12 h.

10. The method for synthesizing multi-substituted olefin compounds by olefin coupling according to claim 9, 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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