CN109796297B - 1, 3-conjugated diene compound, preparation method and application thereof - Google Patents

Abstract

The invention discloses a 1, 3-conjugated diene compound, a preparation method and application thereof. The present invention provides a method for preparing a 1, 3-conjugated diene compound, comprising the steps of: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand and an alkaline reagent, carrying out 1,4-Pd migration/suzuki coupling reaction shown in the specification on an aromatic halide containing a structural fragment shown in a formula I and an alkenyl boron compound containing a structural fragment shown in a formula II to obtain a compound containing a structural fragment of the 1, 3-conjugated diene shown in a formula III. The preparation method has high stereoselectivity and product configurationThe unity; the substrate universality is good, and the electron-deficient olefin, the electron-rich olefin and the polysubstituted olefin can be compatible; and has the characteristics of mild reaction conditions, wide functional group compatibility and the like. The 1, 3-butadiene compound provided by the invention can realize a higher aggregation-induced emission effect.

Description

1, 3-conjugated diene compound, preparation method and application thereof

Technical Field

The invention relates to a 1, 3-conjugated diene compound, a preparation method and application thereof.

Background

The 1, 3-conjugated diene backbone is widely found in natural products (a. vasas, j. hohmann, nat. prod. rep.2011,28,824; e.means, j. sauri, y. liu, a. moser, t.r. ramahar, m.varlan, r.t. williamson, g.e.martin, j.clardy, j.am. chem. soc.2016,138,12324.) and in active drug molecules (o.saku, h.ishida, e.atsumi, y.sugimoto, h.kodaira, y.kato, s.shirakura, y.nakamedo, j.chem.2012, 55,3436; a.

L.wimmer, d.goldmann, s.khom, j.hintersteiner, i.baburin, t.schwarz, m.hintersteiner, p.pakfeifer, m.oufir, m.hamburger, t.erker, g.f.ecker, m.d.mihovovilovic, s.hering, j.med.chem.2014,57,5602.) are also of interest to scientists because of their unique optical properties.

For example, polyaryl substituted 1, 3-butadiene (MPB) and its derivatives are compounds with Aggregation Induced Emission (AIE)/aggregation induced fluorescence enhancement (AEE) effects, and have wide application in chemical detection (such as ion detection (Sens. activators B2018, 267, 351-. Among them, optical properties of 1,1,4, 4-tetraaryl-substituted 1, 3-butadiene (TPB) and 1,1,2,3,4, 4-hexaaryl-substituted 1, 3-butadiene (HPB) have been studied more intensively. However, due to the limitations of synthetic methodology, the optical properties of 1,1, 4-triaryl substituted 1, 3-butadiene have been relatively poorly studied. The structure determines the properties, and slight changes in the structure of a compound may have a great influence on various properties of the compound. Cis-trans isomerism of carbon-carbon double bonds may also affect the properties of such compounds. Therefore, the research on the influence of the double bond Z/E of the 1,1, 4-triaryl substituted 1, 3-butadiene on the optical property is very important.

The methods for synthesizing polysubstituted 1, 3-conjugated dienes currently known are: direct cross-coupling of two different terminal olefins by C-H bond activation under transition metal catalysis gives a 1, 3-conjugated diene backbone (x.shang, z. — q.liu, chem.soc.rev.2013,42,3253; c.liu, j.yuan, m.gao, s.tang, w.li, r.shi, a.lei, chem.rev.2015,115, 12138.). Although this method has a high atom utilization rate, the control of the stereochemistry of two double bonds is still a problem to be solved.

Currently there are two main strategies that can solve the problem of double bond stereochemistry: 1) the stereoselectivity of the double bond is regulated by substrate steric hindrance (z. -k.wen, y. -h.xu, t. -p.loh, chem.sci.2013,4,4520; x. -m.zhong, g. -j.cheng, p.chen, x.zhang, y. -d.wu, org.lett.2016,18,5240.); 2) the stereoselectivity of the product was regulated by targeting groups such as ester groups, amides, etc. (r.feng, w.yu, k.wang, z.liu, y.zhang, adv.synth.catal.2014,356, 1501; x. -h.hu, j.zhang, x. -f.yang, y. -h.xu, t. -p.loh, j.am.chem.soc.2015,137, 3169; c.yu, f.li, j.zhang, g.zhong, chem.commun.2017,53,533.).

The above method has the following disadvantages: 1) for a substrate with smaller steric hindrance difference at two sides of the double bond, the stereochemistry of the double bond cannot be regulated and controlled through the steric hindrance effect of the substrate; 2) there is great difficulty in regulating the stereochemistry of the double bond without a directing group or as opposed to the stereochemistry of the double bond with a directing group. Therefore, the development of a method for synthesizing the polysubstituted 1, 3-conjugated diene with wide substrate universality and stereospecificity is particularly important.

Palladium migration reactions are a special class of C-H bond activation reactions, such as: 1,5-Pd migration reaction or 1,4-Pd migration reaction; they can be classified according to the difference in migration sites: aryl-aryl migration, alkenyl-aryl migration, aryl-alkenyl migration, alkyl-aryl migration, aryl-alkyl migration, and the like.

In 2002, the Larock group captured aryl-to-aryl migration Heck coupled products in a Heck reaction, such as: formula 3 (R.C. Larock, J.Am.chem.Soc.,2002,124,14326). Although migratory products were obtained, the authors only obtained migratory Heck coupled products in yields up to 50% (i.e. migratory product: non-migratory product ═ 1:1), and failed to obtain migratory products with high selectivity. In addition to capture by Heck reaction, capture by arylboronic acids can also be used (i.e. Suzuki reaction). In 2007, the group first achieved aryl to aryl palladium migration/Suzuki coupling reactions, such as: formula 4 (R.C. Larock, J.Am.chem.Soc.,2007,129,6298). Finally, the migration ratio can only be adjusted to 1:1 by optimizing the conditions. In the work of the Larock group, there are two selectivities, migratory and non-migratory, when sodium bicarbonate is used as base (Procedure A), no migration takes place and 100% yield gives the non-migratory product (Table 1, Entry 1); when cesium pivalate is used as the base (original document Procedure C), migration processes occur, but the control of migration ratio is poor, the highest migration: the migration-free ratio is 1:1 (original document Table 1, Entry 6). In this small group of works, the electronic effects have little influence on the migration process.

In addition, Gallagher also performed a related work, in the working group of Gallagher, the original benzene ring was replaced with a pyridine ring, but the mobility ratio could not be controlled, when the substituent R on the benzene ring is an electron-withdrawing group nitro group, the ratio of the mobility was 1:3, when R is an electron-donating group methoxy group, the ratio of the mobility was 1:10, and no matter what substituent, the number of non-migrating products was in the majority. Furthermore, there is still no current debate as to why migration occurs, and how the migration ratio is controlled. (org. Lett.,2002,18, 3115-3118).

In the work of the Larock group, the 1,4-Pd migration/Heck reaction process went through: oxidative addition of aryl iodide species 1 with metallic Pd to form aryl palladium species 2 followed by aryl palladium species 3 by migration of the 1,4-Pd aryl to aryl direction, respectively, by Heck reaction of aryl palladium species 2,3, respectively, can yield compounds 4 and 5, respectively. And the aryl palladium intermediates 2 and 3 are captured by aryl boric acid to obtain Suzuki coupling products 6 and 7 respectively.

Since the 1,4-Pd migration rate of aryl-aryl is lower than the insertion rate of alkenyl in Heck reaction and the transmetallation rate of arylboronic acid in Suzuki reaction, the ratio of migrated to non-migrated products in the reaction depends mainly on the ratio between non-migrated arylpalladium species 2 in the reaction and migrated arylpalladium species 3. The difference in activity between the alkenyl group in the Heck reaction and the arylboronic acid in the Suzuki reaction is not significant in the intermediates 2 and 3 for capturing the migration of 1,4-Pd of the aryl-aryl group, and has no significant effect on the ratio of the migration to the non-migration in the reaction. The balance of the ratio between non-migrating and migrating compounds 2 and 3 may depend on whether the substituents on the phenyl ring are electron withdrawing or electron donating, as well as steric effects. Therefore, the 1,4-Pd migration of the aryl-aryl is applicable to both Heck reaction and Suzuki reaction, the activity of the capture reagents of the intermediates 2 and 3 is not required, and the migration ratio cannot be controlled well in both reactions.

Because arylpalladium species are more stable than alkenylpalladium species and more stable than alkylpalladium species, alkenyl-aryl migration (Tian, Q.; Larock, R.C., Organic Letters 2000,2(21), 3329-; the migration reaction of aryl group to alkenyl group is more difficult to obtain alkenyl palladium species with higher activity by migration of aryl palladium species.

In 2018, the group developed a group of 1,4-Pd migration/Heck reaction, which can synthesize 1, 3-conjugated dienes with a certain stereoselectivity, and some electron-deficient conjugated dienes can be obtained smoothly by the method, such as: formula 5 (T. -J.Hu, C. -G.Feng, G. -Q.Lin, Angew.chem.int.Ed.2018,57,5871.).

However, the synthesis of 1, 3-conjugated dienes by the 1,4-Pd migration/Heck reaction has the following limitations:

1) on one hand, as beta-H in the Heck reaction process is eliminated, only a mixture of cis-trans isomers can be obtained, and a single cis-isomer or trans-isomer cannot be obtained; on the other hand, there is selectivity in β -H elimination, only a mixture of cis-trans isomers, predominantly trans products, is obtained in a ratio of about 10: 1; a Heck reaction product mainly comprising cis-isomer can not be obtained under control; as shown in the following formula, the trans-product is mainly used, wherein the ratio of 3:4 is 92:8, and under all conditions, the trans-product with 4 as the main product is not obtained;

2) the substrate has limitations for electron deficient olefins (as shown below: methyl acrylate, etc.) can be prepared to give the desired compound, but electron rich olefins (e.g.: styrene, etc.) cannot achieve the reaction; none of the sterically hindered olefins can participate in the reaction, etc.

However, from mechanistic analysis, it is more difficult to try to prepare 1, 3-conjugated diene skeletons using the scheme of aryl-alkenyl 1,4-Pd migration combined with Suzuki reaction as follows:

1) possible routes during the 1,4-Pd migration/Suzukiheck reaction: the aryl palladium species 2 is obtained by oxidation addition of an aryl bromine substrate containing terminal double bonds and zero-valent palladium, and then two ways are provided; 1) the aryl palladium species 2 is subjected to transmetallization and reduction elimination to obtain an untransferred product 8; 2) the aryl palladium species 2 is activated by a carbon-hydrogen bond and is transferred by 1, 4-palladium to obtain an alkenyl palladium species 4, and then the alkenyl palladium species and an alkenyl boron reagent are subjected to transmetalization and reduction elimination to obtain a transfer product 6.

We have found that the reaction process for the aryl to alkenyl migration is significantly different from the Heck reaction and the Suzuki reaction of the Larock group described above for aryl to aryl migration.

The alkenyl boron reagent as a high-activity transmetallization reagent has the reaction activity far higher than that of an alkenyl reagent in a Heck reaction, and the transmetallization rate of the alkenyl boron reagent is far higher than that of an aryl boron reagent in a Suzuki reaction that aryl of a Larock group migrates to aryl. Thus, the migration rate of palladium and the Suzuki transition metal rate directly influence the mobility ratio. If the palladium migration rate is higher than the metal transfer rate of Suzuki, generating a migration/Suzuki product; if the palladium migration rate is lower than the Suzuki to metal rate, an untransferred/Suzuki product is formed. Therefore, for such reactions, the activity of the capture reagent has a large influence on the migration ratio of such migration reactions.

In the course of the reaction, in the presence of boron alkenyl, it is highly likely that no 1,4-Pd migration occurs and that no migrated Suzuki reaction product is obtained directly, or that a high migration ratio of migrated product is not obtained as in the 1,4-Pd migration/Heck coupling reaction. Therefore, such reactions are relatively difficult.

2) In the 1,4-Pd migration/Suzuki reaction, the substrate aromatic halide does not have Z/E difference per se; the Z/E of one of the double bonds in the prepared 1, 3-conjugated diene skeleton is controlled by the aryl halide of the substrate, but not by the Z/E of the substrate. Other migration paths may exist in the reaction, such as 1,5-Pd migration, so that the product does not have Z/E selectivity, and finally, a single cis-isomer or a single trans-isomer is difficult to obtain.

In 2012, the Hayashi group unexpectedly found 1-10(J Am Chem Soc 2012,134(17),7305-8)) 1,5-Pd migration products when synthesizing Silicon-Stereogenic Dibenzoles (1-9 are blocks) using compounds 1-8.

According to the 1, 5-migration mechanism described above, two possible routes are proposed during the reaction:

possible mechanism of cis-migration

Mechanism of trans-migration potential

Therefore, it is theoretically difficult to finally obtain a single cis-or trans-isomer due to the possible existence of the 1,5-Pd migration pathway as shown above during the reaction.

3) In the case of alkenylboron compounds, although the alkenylboron used has a single configuration, it is possible to isomerize the Z/E of the double bond during the reaction, especially under basic or light conditions, and the desired single cis-or trans-isomer product is still not obtained. As indicated in chem.Mater.2005,17,1287-1289, Z/E isomerization of the double bond of 2, 5-diphenyl-1, 4-distyrylbenzene (DPDSB) takes place:

in conclusion, aryl-alkenyl transport can yield an alkenylpalladium species with a certain Z/E selectivity, thus making such transport reactions of higher value in organic synthesis. Because of the problems described above, it is considered to be more difficult to try 1,4-Pd migration/Suzuki reaction to synthesize 1, 3-conjugated dienes; even if the 1, 3-conjugated diene backbone can be prepared using the scheme of aryl-alkenyl 1,4-Pd migration combined with Suzuki reaction described above; however, the preparation of a single cis-or trans-isomer is not achieved by mechanistic analysis. Therefore, the development of a method for preparing 1, 3-conjugated diene with higher stereoselectivity, which can prepare single cis-isomer or trans-isomer, and which is compatible with electron-deficient olefin, electron-rich olefin, polysubstituted olefin, etc. is still under study.

Disclosure of Invention

The invention aims to solve the technical problem of single stereoselective synthesis method of a 1, 3-conjugated diene compound in the prior art and the defects of insufficient polyaryl substituted 1, 3-butadiene (MPB) and derivatives thereof, and provides the 1, 3-conjugated diene compound, and a preparation method and application thereof. The preparation method of the 1, 3-conjugated diene compound has higher stereoselectivity and product configuration unicity; the substrate universality is good, and the electron-deficient olefin, the electron-rich olefin and the polysubstituted olefin can be compatible; and has the characteristics of mild reaction conditions, wide functional group compatibility and the like. The 1,1, 4-triaryl substituted 1, 3-butadiene and the derivative thereof provided by the invention can realize higher Aggregation Induced Emission (AIE) effect by controlling double bond Z/E, and can be applied to organic electroluminescent devices as organic luminescent materials.

The present invention solves the above-mentioned problems by the following technical means.

The present invention provides a method for preparing a 1, 3-conjugated diene compound, comprising the steps of: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand and an alkaline reagent, carrying out 1,4-Pd migration/suzuki coupling reaction shown in the specification on an aromatic halide containing a structural fragment shown in a formula I and an alkenyl boron compound containing a structural fragment shown in a formula II to obtain a compound containing a structural fragment of 1, 3-conjugated diene shown in a formula III;

wherein X is bromine or iodine;

[B]is composed of

R^aAnd R^bIndependently is H or C₁-C₆Alkyl, or, R^aAnd R^bIs connected with

Together form an unsubstituted or substituted 5-to 6-membered heterocycloalkyl; said substitution means substitution with one or more of the following substituents: c₁～C₆Alkyl or phenyl; when the substituent is plural, the substituents may be the same or different.

Wherein the content of the first and second substances,

represents an unsaturated bond in an aromatic ring.

In the present invention, the organic solvent may be an organic solvent conventional in such reactions in the art, such as an etheric solvent { e.g., Tetrahydrofuran (THF), dioxane (dioxane), diethyl ether (Et) }₂One or more of O), 2-methyl-tetrahydrofuran (2-Me-THF), methyl tert-butyl ether (TBME), and ethylene glycol dimethyl ether (DME), halogenated hydrocarbon solvents (e.g., dichloromethane), amide solvents { e.g., N-Dimethylformamide (DMF) }, aromatic hydrocarbon solvents (e.g., toluene), alcoholic solvents (e.g., N-butanol), and alkane solvents (e.g., N-hexane).

The palladium catalyst may be palladium as is conventional in such reactions in the artCatalysts, e.g. tris (dibenzylideneacetone) dipalladium-chloroform adduct (Pd)₂dba₃·CHCl₃) Palladium chloride (PdCl)₂) Palladium acetate (Pd (OAc)₂) Tetratriphenylphosphine palladium (Pd (PPh)₃)₄) Dichlorodiphenylpalladium (Pd (PPh)₃)₂Cl₂) And dichlorodiphenylenepalladium (Pd (PhCN)₂Cl₂) One or more of; preferably palladium acetate.

The phosphine ligand may be one conventional in reactions of this type in the art, for example tris (2-methoxyphenyl) phosphine (P (2-OMe-Ph)₃) Triphenylphosphine (PPh)₃) Tris (4-methyl-phenyl) phosphine, tris (4-methoxy-phenyl) phosphine, tris (3-methoxy-phenyl) phosphine, tris (2, 6-dimethoxy-phenyl) phosphine, tris (2,4, 6-trimethoxy-phenyl) phosphine, tricyclohexylphosphine (PCy)₃) Tri (tert-butylphosphine) tetrafluoroborate

Benzyl diphenyl phosphine

2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl

Bis-diphenylphosphinomethane (dppm), 1, 2-bis (diphenylphosphino) ethane (dppe), 1, 3-bis (diphenylphosphino) propane (dppp), 1, 4-bis (diphenylphosphino) butane (dppb), 1, 6-bis (diphenylphosphino) hexane, 9-dimethyl-4, 5-bis-diphenylphosphine xanthene (xanthphos), 4, 5-bis (di-tert-butylphosphino) -9, 9-dimethylxanthene (dpp), and mixtures thereof^tBu-xanthphos), 4, 6-bis (diphenylphosphino) phenazine (NiXantPhos), 3- (dicyclohexylphosphino) -1-methyl-2-phenyl-1H-indole (CM-phos), bis (2-diphenylphosphinophenyl) ether (DPEPhos,

)1, 2-bis (diphenylphosphino) benzene

1,1' -bis (diphenylphosphino) ferrocene(dppf) and R- (+) -2,2 '-bis (diphenylphosphino) -1,1' -binaphthyl

Preferably tris (2-methoxyphenyl) phosphine (P (2-OMe-Ph)₃)。

The basic agent may be one conventional in this type of reaction in the art, such as an alkali metal salt { e.g., cesium acetate (CsOAc), cesium fluoride (CsF), cesium carbonate (Cs)₂CO₃) Cesium pivalate (also known as cesium pivalate or cesium pivalate, CsOPiv), cesium trifluoroacetate (CsOCOCOCF)₃) Potassium fluoride (KF) and potassium phosphate (K)₃PO₄) One or more of [ b ], an alkali metal hydroxide (e.g., potassium hydroxide, KOH), and an organic base (e.g., triethylamine), preferably cesium pivalate.

The amount of the organic solvent is not particularly limited as long as the reaction is not affected; in the invention, the molar volume ratio of the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I to the organic solvent can be 0.05 mmol/mL-1 mmol/mL (for example, 0.3 mmol/mL).

The molar ratio of the alkenyl boron compound shown in the formula II to the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I can be 1: 1-5: 1; preferably 2:1 to 3: 1.

The amount of the palladium catalyst may be an amount conventionally used in such reactions in the art, and in the present invention, the molar percentage of the palladium catalyst to the aromatic halide substituted by an ortho-double bond on the aromatic ring shown in formula I may be 2.5 mol% to 10 mol% (e.g., 5 mol%).

The molar ratio of the ligand to the palladium catalyst can be a molar ratio which is conventional in the reactions in the field, and in the invention, the molar ratio of the ligand to the palladium catalyst can be 1: 1-2: 1 which is conventional in the reactions in the field.

The molar ratio of the alkaline reagent to the aromatic halide substituted by the double bond at the ortho position on the aromatic ring shown in the formula I can be 1: 1-5: 1; preferably 2:1 to 3: 1.

The temperature of the reaction may be a temperature conventional in such reactions in the art, for example, from 50 ℃ to 120 ℃, preferably from 70 ℃ to 110 ℃.

The reaction is preferably carried out in an inert atmosphere, which may be an inert atmosphere conventional to such reactions in the art, such as nitrogen and/or argon.

The progress of the reaction can be monitored by detection methods conventional in the art (e.g., TLC, GC, HNMR, or HPLC, etc.), preferably as the end point of the reaction when the disappearance of the compound of formula I is detected. The reaction time is preferably 5min to 6 hours, more preferably 2 hours to 4 hours.

In one embodiment of the invention, when R is^aOr R^bIs C₁-C₆When alkyl, said C₁-C₆Alkyl (e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl) is C₁-C₄The alkyl group of (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl) is preferably methyl or ethyl.

In one embodiment of the invention, when R is^aAnd R^bIs connected with

When taken together form an unsubstituted or substituted 5-to 6-membered heterocycloalkyl group, the 5-to 6-membered heterocycloalkyl group can be

In one embodiment of the invention, when R is^aAnd R^bIs connected with

Together form a substituted 5-to 6-membered heterocycloalkyl, said substitution being C₁-C₆When alkyl, said C₁-C₆Alkyl (e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl) is C₁-C₄Alkyl (e.g., methyl,Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl), preferably methyl.

In one embodiment of the invention, when R is^aAnd R^bIs connected with

Together form a substituted 5-6 membered heterocycloalkyl, which when substituted is phenyl, is cycloconnected to the 5-6 membered heterocycloalkyl.

In one embodiment of the invention, when R is^aAnd R^bIs connected with

Together form a substituted 5-to 6-membered heterocycloalkyl group, the number of substitutions being 1,2,3 or 4.

In one embodiment of the present invention, [ B ] is]Is composed of

When it is used, the

Can be any one of the following structures:

in one embodiment of the present invention, the aromatic halide containing the structural fragment shown in formula I is shown in formula I ', and the alkenyl boron compound containing the structural fragment shown in formula II is shown in formula II ', so as to obtain the compound containing the structural fragment of the 1, 3-conjugated diene shown in formula III ', correspondingly;

wherein the content of the first and second substances,

is optionally substituted C₆-C₁₀Aryl or optionally substituted 5-to 6-membered heteroaryl; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-3;

R²、R³、R⁴and R⁵Independently is H, -CN, -NO₂、-C(＝O)-R^2-1、-C(＝O)-N(R^2-2R^2-3) Optionally substituted C₁-C₆Alkyl, optionally substituted C₃-C₁₀Cycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkenyl, optionally substituted C₆-C₁₀Aryl or optionally substituted 5-to 6-membered heteroaryl; said C₃～C₁₀In the heterocycloalkyl group (b), the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-4; said C₃～C₁₀In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 4; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-4;

or, R³And R⁴Or, R³And R⁵Together with the carbon to which it is directly attached form optionally substituted C₄～C₆Or optionally substituted C₃～C₅The heterocycloalkenyl group of (a); said C₃～C₅In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 2;

said R³And R⁴Or, R³And R⁵Together with the carbon to which it is directly attached form optionally substituted C₄～C₆Or optionally substituted C₃～C₅The heterocycloalkenyl of (1), the

In (1) optionally substituted C₆-C₁₀Aryl or optionally substituted 5-to 6-membered heteroaryl, and said R²、R³、R⁴And R⁵In (1) optionally substituted C₁-C₆Alkyl, optionally substituted C₃-C₁₀Cycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkenyl, optionally substituted C₆-C₁₀In aryl or optionally substituted 5-6 membered heteroaryl, each of said optional substitutions independently is unsubstituted or substituted with one or more of the following substituents, when there are more than one, said substituents are the same or different: H. f, Cl, -NO₂、-OH、-CN、-N(R^1-1R^1-2)、-C(＝O)-R^1-3、-O-C(＝O)-R^1-4、-N(R^1-5)-C(＝O)-R^1-6、-C(＝O)-N(R^1-7R^1-8)、-O-C(＝O)-N(R^1-9R^1-10)、-S(＝O)-N(R^1-11R^1-12)、-S(＝O)₂-N(R^1-13R^1-14) Unsubstituted or substituted C₁～C₆Alkyl, unsubstituted or substituted C₁～C₆alkyl-O-, unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, unsubstituted or substituted C₃-C₆Cycloalkyl, unsubstituted or substituted C₃-C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkenyl, unsubstituted or substituted C₆-C₁₀Aryl, or unsubstituted or substituted 5-to 6-membered heteroaryl; said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-4; said C₃～C₅In the heterocycloalkenyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-4; said substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In the aryl or the substituted 5-6-membered heteroaryl, the substitution is independently one or more of the following substituents, and when the substituents are multiple, the substituents are the same or different: F. cl, -NO₂、-OH、-CN、-C(＝O)H、-COOH、-NH₂、-C(＝O)NH₂、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O (i.e., two gem-hydrogens on carbon atoms are substituted with groups O);

R^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13and R^1-14Independently is H, unsubstituted or substituted C₁～C₆Alkyl, unsubstituted or substituted C₁～C₆alkyl-O-, unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, unsubstituted or substituted C₃～C₆Cycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkenyl, unsubstituted or substituted phenyl, or unsubstituted or substituted 5-to 6-membered heteroaryl; said C₃～C₅In the heterocycloalkyl group, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3; said C₃～C₅In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 3; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-3; said substituted C₁～C₆Alkyl, said substituted C₁～C₆alkyl-O-, said substitutionC of (A)₂～C₆Alkenyl, said substituted C₂～C₆alkenyl-O-, said substituted C₃～C₆Cycloalkyl, said substituted C₃～C₅Heterocycloalkyl, said substituted C₃～C₅In heterocycloalkenyl, the substituted phenyl, or the substituted 5-to 6-membered heteroaryl, the substitutions each independently refer to one or more of the following substituents: F. cl, -OH, -CF₃、-CN、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O; when the number of the substituents is plural, the substituents may be the same or different;

or, R^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅The heterocycloalkenyl group of (a), or the unsubstituted or substituted 5-to 6-membered heteroaryl group; said C₃～C₅In the heterocyclic alkyl, the heteroatom is nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-3; said C₃～C₅In the heterocycloalkenyl, the heteroatoms are nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-3; in the 5-6-membered heteroaryl, the heteroatoms are nitrogen, or nitrogen, oxygen and/or sulfur, and the number of the heteroatoms is 1-3; said substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅In the heterocycloalkenyl group or the substituted 5-to 6-membered heteroaryl group, the substitution is independently one or more of the following substituents: F. cl, -OH, -CF₃、-CN、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O; when the substituent is plural, the substituents may be the same or different.

In the present invention, the definition of some substituents in the 1, 3-conjugated diene compound represented by formula III' may be as follows, and the definition of the substituents which are not mentioned is as described in any of the above schemes.

In one embodiment of the present invention, when said

Is optionally substituted C₆-C₁₀When aryl, said C₆-C₁₀Aryl is phenyl.

In one embodiment of the present invention, when said

And when the aryl group is an optionally substituted 5-6-membered heteroaryl group, the 5-6-membered heteroaryl group contains 2-5 carbon atoms, wherein the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-3.

In one embodiment of the present invention, when said

Is optionally substituted C₆-C₁₀In the aryl or the optionally substituted 5-6 membered heteroaryl, the number of substitution is 1,2,3 or 4.

In one embodiment of the present invention, when said

Is optionally substituted C₆-C₁₀In the aryl or the optionally substituted 5-6 membered heteroaryl, the substituted position is the alpha position, the beta position, the gamma position or the delta position of the X.

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₁-C₆When alkyl, said C₁～C₆Alkyl (e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl) is C₁～C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl), preferably methyl, ethyl or n-propyl.

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When there is a cycloalkyl group, said C₃-C₁₀Cycloalkyl being C₃-C₆Cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl).

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When it is heterocycloalkyl, said C₃-C₁₀Heterocycloalkyl being C₃-C₅Heterocycloalkyl radical of said formula C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3.

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When it is heterocyclenyl, said C₃-C₁₀Heterocycloalkenyl is C₃-C₅Heterocycloalkenyl group of said C₃-C₅In the heterocycloalkenyl group, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1 to 3.

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₆-C₁₀When aryl, said optionally substituted C₆-C₁₀Aryl is phenyl or naphthyl (e.g. phenyl

)。

In one embodiment of the present invention, when said R is²、R³、R⁴Or R⁵In the case of an optionally substituted 5-6 membered heteroaryl group, the optionally substituted 5-6 membered heteroaryl group has 1-2 hetero atoms, such as a thienyl group (for example), and one or more hetero atoms of N, O and S

)。

In one embodiment of the present invention, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₄～C₆Cycloalkenyl of (a), C₄～C₆Cycloalkenyl of (a) is cyclopentenyl (e.g. cyclopentenyl)

) Or cyclohexenyl (e.g. cyclohexenyl)

)。

In one embodiment of the present invention, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₃～C₅When said heterocycloalkenyl group is (a), said C₃～C₅The heterocycloalkenyl group of (a) is a 2H-pyranyl group (e.g. 3, 6-dihydro-2H-pyranyl group, further e.g.

)。

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl (e.g. methyl, ethyl, propyl, butyl, pentyl or hexyl) is C₁～C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl), preferably methyl.

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₂～C₆Alkenyl, or unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is C₂-C₄Alkenyl { e.g., ethenyl, propenyl (e.g., 1-propenyl or 2-propenyl), or butenyl (e.g., as2-butenyl, 1-butenyl, or butadiene).

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₃-C₆When there is a cycloalkyl group, said C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₃-C₅When it is heterocycloalkyl, said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3.

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₃-C₅When it is heterocyclenyl, said C₃-C₅In the heterocycloalkenyl group, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1 to 3.

In one embodiment of the present invention, when said optionally substituted substituent is unsubstituted or substituted C₆-C₁₀When aryl, said optionally substituted C₆-C₁₀Aryl is phenyl or naphthyl.

In one embodiment of the present invention, when the optionally substituted substituent is an unsubstituted or substituted 5-6 membered heteroaryl group, the number of heteroatoms in the optionally substituted 5-6 membered heteroaryl group is one or more of N, O and S, and the number of heteroatoms is 1-2.

In one embodiment of the present invention, when said substituent in said optional substitution is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In aryl or substituted 5-to 6-membered heteroaryl, said substitution is C₁～C₆Alkyl or C₁～C₆alkyl-O-said C₁～C₆Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl) is independently C₁～C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl).

In one embodiment of the present invention, when said substituent in said optional substitution is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In the aryl or the substituted 5-6-membered heteroaryl, the number of the substitution is 1,2,3 or 4.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is unsubstituted or substituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl) is independently C₁～C₄An alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl), such as methyl or ethyl.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is C₂-C₄An alkenyl group { e.g., an ethenyl group, a propenyl group (e.g., 1-propenyl or 2-propenyl group), or a butenyl group (e.g., 2-butenyl, 1-butenyl, or butadiene) }.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is unsubstituted or substituted C₃～C₆When there is a cycloalkyl group, said C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is unsubstituted or substituted C₃-C₅When it is heterocycloalkyl, said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is unsubstituted or substituted C₃-C₅When it is heterocyclenyl, said C₃-C₅Heterocyclic alkenyl radicalsIn the formula (I), the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14When the aryl group is an unsubstituted or substituted 5-6 membered heteroaryl group, the number of heteroatoms in the optionally substituted 5-6 membered heteroaryl group is one or more of N, O and S, and is 1-2.

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃～C₆Cycloalkyl, substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅In the heterocycloalkenyl group, the substituted phenyl group or the substituted 5-to 6-membered heteroaryl group, the substitution is C₁～C₆Alkyl or C₁～C₆alkyl-O-said C₁～C₆Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl) is independently C₁～C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl).

In one embodiment of the present invention, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13Or R^1-14Is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃～C₆Cycloalkyl, substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅And when the heterocyclic alkenyl group, the substituted phenyl group or the substituted 5-6-membered heteroaryl group is adopted, the number of the substitution is 1,2,3 or 4.

In one embodiment of the present invention, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^{1 -10}、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅When said heterocycloalkyl group is (C)₃～C₅In the heterocycloalkyl group (2), the hetero atoms are nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the hetero atoms is 1 to 2.

In one embodiment of the present invention, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^{1 -10}、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅When said heterocycloalkenyl group is (a), said C₃～C₅The heterocyclic alkenyl group of (2) is a heterocyclic group in which the hetero atom is nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the hetero atom is 1 to 2.

In one embodiment of the present invention, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^{1 -10}、R^1-11And R^1-12Or, R^1-13And R^1-14When the nitrogen atoms are respectively and independently combined with the directly connected nitrogen to form unsubstituted or substituted 5-6-membered heteroaryl, in the 5-6-membered heteroaryl, the heteroatoms are nitrogen, or nitrogen, oxygen and/or sulfur, and the number of the heteroatoms is 1-2.

In one embodiment of the present invention, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^{1 -10}、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently taken together with the nitrogen to which it is directly attached form substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅The heterocycloalkenyl or substituted 5-to 6-membered heteroaryl of (a) wherein the substitution is C₁～C₆Alkyl or C₁～C₆C as described for alkyl-O-, said substitution₁～C₆Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl) is independently C₁-C₄Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl).

In one embodiment of the present invention, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^{1 -10}、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently taken together with the nitrogen to which it is directly attached form substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅When the heterocycloalkenyl group or the substituted 5-to 6-membered heteroaryl group is mentioned, the number of the substitutions is 1,2,3 or 4 independently of each other.

In one embodiment of the invention when said optionally substituted is substituted C₁～C₆When alkyl, said substituted C₁～C₆Alkyl is-CF₃。

In one embodiment of the present invention,

is composed of

In one embodiment of the invention, R²、R³、R⁴Or R⁵Is H, -CN, methyl, ethyl, isopropyl, n-propyl, -C (═ O) -O-CH₃、-C(＝O)-O-C₂H₅、

In one embodiment of the invention, R³And R⁵Together with the carbon-carbon double bond directly attached to form

In one embodiment of the present invention, the above

Can be any one of the following structures:

in one embodiment of the present invention, the aromatic halide represented by formula I' and containing the structural fragment represented by formula I can be any one of the following compounds:

in one embodiment of the present invention, the alkenylboron compound represented by formula II' containing the structural fragment represented by formula II may be any one of the following compounds:

in one embodiment of the present invention, the compound containing the structural fragment of the 1, 3-conjugated diene represented by formula III, as represented by formula III', may be any one of the following compounds:

in one embodiment of the present invention, the structure of the compound containing the structural fragment of the 1, 3-conjugated diene shown in formula III ', the structure of the alkenyl boron compound containing the structural fragment of the formula II shown in formula II', and the structure of the compound containing the structural fragment of the 1, 3-conjugated diene shown in formula III 'obtained in formula III' are as follows:

the invention also provides an application of the 1, 3-butadiene compound shown as the formula X as an organic electroluminescent material,

wherein R is^X1、R^X2、R^X3、R^X4、R^X5、R^X6、R^X7、R^X8、R^X9、R^X10、R^X11、R^X12、R^X13、R^X14And R^X15Independently H or F.

In a solution of the application of the invention,

the double bond in (A) may be in the E configuration, Z configuration or not in the E/Z configuration, preferably in the E configuration or not in the E/Z configuration, more preferably in the E configuration.

In a certain technical scheme of the application of the invention, the 1, 3-butadiene compound shown as the formula X has a structure shown as any one of the following compounds:

the invention provides a 1, 3-butadiene compound shown as a formula X',

wherein R is^X1’、R^X2’、R^X3’、R^X4’、R^X5’、R^X6’、R^X7’、R^X8’、R^X9’、R^X10’、R^X11’、R^X12’、R^X13’、R^X14’And R^X15’Independently H or F, but not both.

In a certain aspect of the present invention,

the double bond in (A) may be in the E configuration, Z configuration or not in the E/Z configuration, preferably in the E configuration or not in the E/Z configuration, more preferably in the E configuration.

In a certain technical scheme of the invention, the 1, 3-butadiene compound shown in the formula X' has a structure shown in any one of the following compounds:

definitions and general terms

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.

The following definitions as used herein should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.

The term "comprising" is open-ended, i.e. comprising what is specified in the invention, but does not exclude other aspects.

In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Further, when the group is substituted with 1 or more of the substituents, the substituents are independent of each other, that is, the 1 or more substituents may be different from each other or the same. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of the substituted group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently.

In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C₁～C₆Alkyl "or" C_1-6Alkyl "means in particular independently disclosed methyl, ethyl, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl and C₆An alkyl group; "C_1-4Alkyl refers specifically to independently disclosed methyl, ethyl, C₃Alkyl (i.e. propyl, including n-propyl and isopropyl), C₄Alkyl (i.e., butyl, including n-butyl, isobutyl, sec-butyl, and tert-butyl).

In each of the parts of the invention, linking substituents are described. Where the structure clearly requires a linking group, the markush variables listed for that group are understood to be linking groups. For example, if the structure requires a linking group and the markush group definition for the variable recites "alkyl" or "aryl," it is understood that the "alkyl" or "aryl" represents an attached alkylene group or arylene group, respectively.

The term "alkyl", as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon radical containing from 1 to 20 carbon atoms, wherein the alkyl radical may be optionally substituted with one or more substituents described herein. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3, 3-dimethyl-2-butyl, n-heptyl, n-octyl, and the like.

In some specific structures, when an alkyl group is expressly indicated as a linking group, then the alkyl group represents a linked alkylene group, e.g., the group "halo-C₁～C₆C in alkyl₁-C₆Alkyl is understood to mean C₁～C₆An alkylene group.

The term "alkylene" refers to a saturated divalent hydrocarbon radical resulting from the removal of two hydrogen atoms from a saturated straight or branched chain hydrocarbon radical. Examples of alkylene groups include methylene (-CH)₂-, ethylene (including-CH)₂CH₂-or-CH (CH)₃) -, isopropylidene (including-CH (CH)₃)CH₂-or-C (CH)₃)₂-) and the like.

The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp²Double bonds, which include the positioning of "cis" and "tan", or the positioning of "E" and "Z". Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)₂) Allyl (-CH)₂CH＝CH₂) And so on.

The term "alkoxy" or "alkyl-O-" means that the alkyl group is attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-propoxy, 2-propoxy, 1-butoxy, and the like.

The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, or bicyclic, ring system containing 3 to 12 ring carbon atoms. Examples of cycloalkyl radicalsExamples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like; wherein, said C₃-C₆Cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "heterocycloalkyl" refers to a saturated monocyclic, or bicyclic ring system containing 3 to 12 ring atoms, at least one of which is selected from nitrogen, sulfur and oxygen. Unless otherwise indicated, heterocycloalkyl can be carbon or nitrogen based, and-CH₂-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atoms of the ring may optionally be oxidized to the N-oxide. In some embodiments, heterocycloalkyl is C₃～C₅Heterocycloalkyl, meaning a heterocyclyl group containing from 3 to 5 ring carbon atoms and at least one ring heteroatom selected from O, S and N. Examples of heterocyclyl groups include, but are not limited to: oxiranyl, thietanyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, oxazolidinyl, tetrahydrofuranyl, piperidinyl, morpholinyl, tetrahydropyrimidinyl, oxazinidinyl, thiomorpholinyl, piperazinyl, and the like. In heterocyclic radicals of-CH₂Examples of the substitution of the-group by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, 2-piperidinonyl, 3-morpholinonyl, 3-thiomorpholinonyl, oxotetrahydropyrimidinyl and the like.

The term "heterocycloalkenyl" refers to a monocyclic, or bicyclic, system containing 3-12 ring atoms containing a partially unsaturated alkenyl group, wherein at least one ring atom is selected from the group consisting of nitrogen, sulfur, and oxygen atoms; wherein the heterocycloalkenyl is non-aromatic and does not contain any aromatic rings. Unless otherwise specified, a heterocycloalkenyl group can be carbon-based or nitrogen-based, and-CH₂-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atoms of the ring may optionally be oxidized to the N-oxide.

The term "aryl" denotes monocyclic, bicyclic and tricyclic carbocyclic ring systems containing 6 to 14 ring atoms, or 6 to 10 ring atoms. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenylNaphthyl and anthracenyl. Unless otherwise stated, the group "C₆-C₁₀Aryl "represents an aryl group containing from 6 to 10 ring carbon atoms.

The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 6 ring atoms, or 5 to 10 ring atoms, or 5 to 12 ring atoms, wherein at least one ring contains one or more ring heteroatoms selected from nitrogen, oxygen, sulfur. Unless otherwise indicated, the heteroaryl group may be attached to the rest of the molecule (e.g., the main structure in the general formula) via any reasonable site (which may be C in CH, or N in NH). Examples include, but are not limited to, furyl, imidazolyl, isoxazolyl, oxazolyl, pyrrolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, thiazolyl, and the like; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzothienyl, indolyl, oxoindolyl, imidazopyridinyl, pyrazolopyridinyl, pyrazolopyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and the like.

In addition, it should be noted that, unless otherwise explicitly indicated, the description of "… independently" as used herein is to be understood in a broad sense to mean that each individual entity so described is independent of the other and may be independently the same or different specific groups. In more detail, the description "… is independently" can mean that the specific options expressed between the same symbols do not affect each other in different groups; it can also be said that in the same group, the specific options expressed between the same symbols do not affect each other.

It will be understood by those skilled in the art that, in accordance with the convention used in the art, the structural formulae used in the radicals described herein

Means that the corresponding group is linked to other fragments, groups in the compound through this site.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: the preparation method of the 1, 3-conjugated diene compound has high stereoselectivity and product configuration unicity; the substrate universality is good, and the electron-deficient olefin, the electron-rich olefin and the polysubstituted olefin can be compatible; and has the characteristics of mild reaction conditions, wide functional group compatibility and the like.

Drawings

FIG. 1 shows a single crystal structure of compound 3ba in example 10.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

Example 1

Synthesis of compound 3 aa:

to a dry Schlenk tube, 1.7mg of Pd (OAc) was added under argon atmosphere₂，5.3mg P(2-OMe-Ph)₃78mg 1aa (0.3mmol), 98mg 2aa (0.6mmol), 141mg CsOPiv, 3mL THF, warm to 70 ℃ and stir for 1 h. Quenching the reaction with 5mL of saturated ammonium chloride aqueous solution, extracting with 5mL of ethyl acetate for three times, washing the organic phase with saturated NaCl solution, drying the anhydrous sodium sulfate solid, concentrating, performing column chromatography with n-hexane as an eluent, and collecting the product band to obtain 80.5mg of a 3aa white solid with a yield of 95%.

¹H NMR(400MHz,CDCl₃)δ7.47–7.37(m,3H),7.34–7.23(m,11H),7.18(t,J＝7.1Hz,1H),6.95–6.83(m,2H),6.74(dt,J＝10.8,7.4Hz,1H)；EI-MS m/z(％):282(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₉[M+H]⁺:283.1481,found:283.1481.

Example 2

Synthesis of compound 3 ab:

starting from 1ab, the procedure is as in example 1, with a yield of 98%.

¹H NMR(400MHz,CDCl₃)δ7.35–7.22(m,10H),7.18(t,J＝7.0Hz,2H),7.09(d,J＝9.3Hz,2H),6.95–6.83(m,2H),6.78–6.67(m,1H),2.38(s,3H)；¹³C NMR(100MHz,CDCl₃)δ143.46,142.50,139.83,137.98,137.69,133.81,131.26,128.70,128.38,128.34,128.29,128.22,127.92,127.73,127.59,127.55,127.40,126.60,21.63；EI-MS m/z(％):296(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₃H₂₁[M+H]⁺:297.1638,found:297.1638.

Example 3

Synthesis of compound 3 ac:

starting from 1ac, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.34–7.14(m,14H),6.94(dd,J＝15.3,10.9Hz,1H),6.84(d,J＝11.0Hz,1H),6.72(d,J＝15.3Hz,1H),2.43(s,3H)；¹³C NMR(100MHz,CDCl₃)δ143.35,142.70,137.73,137.35,136.91,133.74,130.70,129.07,128.69,128.31,128.23,127.83,127.55,127.54,127.45,126.58,21.47；EI-MS m/z(％):296(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₃H₂₁[M+H]⁺:297.1638,found:297.1638.

Example 4

Synthesis of compound 3 ad:

starting from 1ad, the procedure is as in example 1, with a yield of 97%.

¹H NMR(400MHz,CDCl₃)δ7.38(td,J＝7.9,6.2Hz,1H),7.34–7.16(m,10H),7.11–7.04(m,2H),6.99(dd,J＝9.8,1.7Hz,1H),6.90–6.81(m,2H),6.80–6.71(m,1H)；¹³C NMR(100MHz,CDCl₃)δ162.90(d,J＝246.4Hz),142.17(d,J＝7.6Hz),141.80,141.78,137.41,134.65,129.89(d,J＝8.4Hz),128.92,128.75,128.47,127.86,127.79,127.61,126.67,126.56(d,J＝2.9Hz),117.56(d,J＝21.2Hz),114.61(d,J＝21.0Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-113.22；EI-MS m/z(％):300(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈F[M+H]+:301.1387,found:301.1387.

Example 5

Synthesis of compound 3 ae:

starting with 1ae, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.34–7.16(m,12H),7.15–7.08(m,2H),6.90–6.80(m,2H),6.79–6.71(m,1H)；¹³C NMR(100MHz,CDCl₃)δ162.37(d,J＝246.7Hz),142.25,142.11,137.51,135.81(d,J＝3.4Hz),134.33,132.41(d,J＝7.9Hz),128.76,128.67,128.44,127.78,127.75,127.67,126.90,126.60,115.41(d,J＝21.3Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-114.49；EI-MS m/z(％):300(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈F[M+H]+:301.1387,found:301.1387.

Example 6

Synthesis of compound 3 af:

starting from 1af, the procedure is described in example 1 with a yield of 71%.

¹H NMR(400MHz,CDCl₃)δ7.40(d,J＝8.4Hz,2H),7.34–7.24(m,9H),7.21(dd,J＝11.9,5.3Hz,3H),6.87(s,1H),6.85(q,J＝10.4Hz,1H),6.74(dq,J＝10.0,2.8Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ142.01,141.88,138.38,137.43,134.63,133.55,132.14,128.85,128.77,128.68,128.46,127.85,127.80,127.69,126.71,126.64；EI-MS m/z(％):316(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈Cl[M+H]+:317.1092,found:317.1090.

Example 7

Synthesis of Compound 3 ag:

starting with 1ag, the procedure is described in example 1, with a yield of 88%.

¹H NMR(400MHz,CDCl₃)δ7.69(d,J＝8.1Hz,2H),7.41(d,J＝8.0Hz,2H),7.36–7.24(m,10H),7.24–7.16(m,1H),6.93(dd,J＝7.8,2.6Hz,1H),6.84–6.74(m,2H)；¹³C NMR(100MHz,CDCl₃)δ143.74,141.70,141.54,137.25,135.29,131.10,129.72(q,J＝270.7Hz),129.37,128.79,128.54,128.00,127.91,127.65,126.70,126.28,125.41(q,J＝3.8Hz),124.37(q,J＝32.2Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-62.43；EI-MS m/z(％):350(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₃H₁₇F₃[M]+:350.1282,found:350.1273.

Example 8

Synthesis of compound 3 ah:

starting from 1ah, the procedure is as in example 1, with a yield of 90%.

¹H NMR(400MHz,CDCl₃)δ7.35–7.23(m,9H),7.23–7.15(m,3H),6.99–6.89(m,3H),6.82(d,J＝11.0Hz,1H),6.72(d,J＝15.4Hz,1H),3.87(s,3H)；¹³C NMR(100MHz,CDCl₃)δ159.15,143.05,142.81,137.75,133.59,132.23,132.01,128.70,128.32,128.10,127.87,127.57,127.54,127.49,126.54,113.75,55.42；EI-MS m/z(％):312(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₃H₂₀O[M]+:312.1514,found:312.1509.

Example 9

Synthesis of compound 3 ai:

starting from 1ai, the procedure is as in example 1, 91% yield.

¹H NMR(400MHz,CDCl₃)δ7.37–7.17(m,11H),7.14–7.05(m,1H),7.05–6.99(m,1H),6.91–6.72(m,3H)；¹³C NMR(100MHz,CDCl₃)δ150.22(dd,J＝247,5,40.0Hz),150.10(dd,J＝248.0,40.0Hz),141.67,140.88,137.30,136.83(dd,J＝5.7,4.0Hz),135.07,129.18,128.81,128.54,127.99,127.94,127.59,127.00(dd,J＝6.1,3.5Hz),126.68,126.34,119.59(d,J＝16.9Hz),117.29(d,J＝17.1Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-137.72,-139.02；EI-MS m/z(％):318(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₂H₁₆F₂[M]+:318.1220,found:318.1226.

Example 10

Synthesis of Compound 3 ba:

see example 1 for operation with 91% yield starting from 1 ba.

¹H NMR(400MHz,CDCl₃)δ7.37(t,J＝7.3Hz,4H),7.34–7.25(m,6H),7.25–7.19(m,4H),7.16(m,1H),6.72(d,J＝15.6Hz,1H),6.50(d,J＝11.1Hz,1H),2.05(s,3H)；¹³C NMR(101MHz,CDCl₃)δ143.71,143.53,140.42,137.65,136.64,134.24,130.64,130.56,130.37,130.04,128.74,128.26,127.64,127.62,127.36,126.63,126.61,125.75,20.78.

The single crystal structure of compound 3ba showed a single configuration for both of its double bonds, i.e. (E, E).

Example 11

Synthesis of compound 3 bb:

starting from 1bb, the procedure is as in example 1, yield 86%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.34(m,3H),7.28(ddd,J＝13.3,9.1,7.1Hz,6H),7.18(dt,J＝7.0,4.6Hz,2H),7.14(s,1H),7.11–7.04(m,2H),6.94–6.82(m,2H),6.78–6.67(m,1H),2.32(s,3H)；¹³C NMR(100MHz,CDCl₃)δ143.42,142.44,140.00,137.90,137.67,133.84,130.78,128.70,128.43,128.37,128.33,128.31,128.25,127.59,127.58,127.31,126.57,125.03,21.63；EI-MS m/z(％):296(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₃H₂₁[M+H]⁺:297.1638,found:297.1637.

Example 12

Synthesis of compound 3 bc:

starting from 1bc, the procedure is described in example 1, with a yield of 97%.

¹H NMR(400MHz,CDCl₃)δ7.45–7.33(m,3H),7.33–7.23(m,6H),7.18(dd,J＝16.2,7.7Hz,3H),7.11(d,J＝8.0Hz,2H),6.94–6.80(m,2H),6.76–6.66(m,1H),2.34(s,3H)；¹³C NMR(100MHz,CDCl₃)δ143.25,140.07,139.61,137.73,137.52,133.54,130.77,129.10,128.69,128.33,127.64,127.62,127.56,127.53,127.38,126.54,21.30；EI-MS m/z(％):296(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₃H₂₁[M+H]⁺:297.1638,found:297.1638.

Example 13

Synthesis of compound 3 bd:

starting from 1bd, the procedure is as in example 1, with a yield of 96%.

¹H NMR(400MHz,CDCl₃)δ7.48–7.36(m,3H),7.34–7.23(m,7H),7.20(dd,J＝12.3,5.1Hz,1H),7.08(d,J＝7.8Hz,1H),7.03–6.91(m,2H),6.91–6.82(m,2H),6.76(dt,J＝10.9,7.2Hz,1H)；¹³C NMR(101MHz,CDCl₃)δ162.99(d,J＝245.0Hz),144.73(d,J＝7.6Hz),142.00,139.32,137.43,134.83,130.69,129.70(d,J＝8.4Hz),129.26,128.74,128.52,127.86,126.88,126.69,123.32(d,J＝2.7Hz),114.48(d,J＝10.7Hz),114.27(d,J＝9.9Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-113.63(s).

Example 14

Synthesis of Compound 3 be:

starting from 1be, the procedure is as in example 1, 89% yield.

¹H NMR(400MHz,CDCl₃)δ7.46–7.38(m,3H),7.34–7.17(m,11H),6.92–6.81(m,2H),6.80–6.72(m,1H)；¹³C NMR(100MHz,CDCl₃)δ142.00,140.92,139.46,137.48,134.53,133.39,130.69,128.94,128.74,128.52,128.52,127.85,127.80,126.98,126.65；EI-MS m/z(％):316(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₇Cl[M]⁺:316.1013,found:316.1013.

Example 15

Synthesis of compound 3 bf:

starting from 1bf, the procedure is as in example 1, with a yield of 87%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.35(m,3H),7.33–7.22(m,8H),7.18(t,J＝7.0Hz,1H),7.02–6.95(m,2H),6.88(dd,J＝15.1,10.8Hz,1H),6.80(d,J＝10.8Hz,1H),6.73(d,J＝15.1Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ162.48(d,J＝247.3Hz),142.18,139.74,138.62(d,J＝3.3Hz),137.55,134.08,130.53,129.17(d,J＝8.0Hz),128.56,128.31,128.06(d,J＝1.5Hz),127.62,127.69,127.09,126.59,115.25(d,J＝21.5Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-114.82；EI-MS m/z(％):300(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈F[M+H]⁺:301.1387,found:301.1387.

Example 16

Synthesis of compound 3 bg:

starting from 1bg, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.54(d,J＝8.3Hz,2H),7.49–7.36(m,4H),7.36–7.24(m,7H),7.21(t,J＝7.0Hz,1H),6.90(q,J＝10.2Hz,2H),6.85–6.74(m,1H)；¹³C NMR(100MHz,CDCl₃)δ145.91,141.75,139.17,137.30,135.46,130.68,130.17,129.30(q,J＝30.1Hz),128.78,128.62,128.02,127.99,127.86,126.76,126.74,125.31(q,J＝3.8Hz),124.39(q,J＝270.6Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-62.47；EI-MS m/z(％):350(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈F₃[M+H]⁺:351.1355,found:351.1355.

Example 17

Synthesis of compound 3 bh:

starting from 1bh, the procedure is as in example 1, 88% yield.

¹H NMR(400MHz,CDCl₃)δ7.46–7.36(m,3H),7.33–7.21(m,8H),7.17(t,J＝7.0Hz,1H),6.92–6.78(m,4H),6.70(d,J＝14.8Hz,1H),3.81(s,3H)；¹³C NMR(100MHz,CDCl₃)δ159.35,142.91,140.12,137.79,135.08,133.09,130.75,128.91,128.68,128.34,127.58,127.46,127.44,126.82,126.48,113.78,55.46；EI-MS m/z(％):312(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₃H₂₁O[M+H]⁺:313,1587,found:313.1587.

Example 18

Synthesis of Compound 3 bi:

starting from 1bi, the procedure is as in example 1, with a yield of 98%.

¹H NMR(400MHz,CDCl₃)δ7.95(d,J＝8.5Hz,1H),7.83(dd,J＝13.6,8.1Hz,2H),7.52–7.17(m,15H),6.70(dd,J＝25.2,13.4Hz,2H)；¹³C NMR(100MHz,CDCl₃)δ142.09,141.77,141.06,137.61,134.62,134.09,132.12,132.03,129.99,128.77,128.39,128.06,127.79,127.75,127.54,126.68,126.62,126.42,126.08,125.76,125.41；EI-MS m/z(％):332(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₆H₂₁[M+H]⁺:333.1638,found:333.1638.

Example 19

Synthesis of compound 3 bj:

starting from 1bj, the procedure is as in example 1, 91% yield.

¹H NMR(400MHz,CDCl₃)δ7.83–7.70(m,3H),7.65(s,1H),7.54(dd,J＝8.6,1.7Hz,1H),7.49–7.37(m,5H),7.36–7.24(m,6H),7.19(t,J＝7.1Hz,1H),7.03(d,J＝10.9Hz,1H),6.94(dd,J＝15.1,10.9Hz,1H),6.79(d,J＝15.1Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ143.23,139.88,139.76,137.63,134.19,133.48,132.93,130.87,128.94,128.73,128.46,128.39,127.88,127.73,127.69,127.66,127.30,127.10,126.63,126.32,126.11,125.56；EI-MS m/z(％):332(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₆H₂₀[M]⁺:332.1565,found:332.1569.

Example 20

Synthesis of compound 3 bk:

starting from 1bk, the procedure is as in example 1, in 88% yield.

¹H NMR(400MHz,CDCl₃)δ7.47–7.39(m,3H),7.38–7.34(m,2H),7.31–7.22(m,4H),7.21–7.14(m,2H),6.96–6.87(m,2H),6.79–6.67(m,3H)；¹³C NMR(100MHz,CDCl₃)δ147.11,138.86,137.57,137.11,133.70,130.34,128.70,128.43,128.01,127.71,127.64,127.10,126.57,126.55,126.27,124.89；EI-MS m/z(％):288(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₀H₁₇S[M+H]⁺:289.1045,found:289.1045.

Example 21

Synthesis of Compound 3 ca:

starting from 1ca, the procedure is as in example 1, with a yield of 86%.

¹H NMR(400MHz,CDCl₃)δ7.38(t,J＝7.3Hz,2H),7.31(d,J＝7.3Hz,1H),7.29–7.20(m,6H),7.18–7.09(m,1H),6.79(dd,J＝15.6,10.9Hz,1H),6.55(d,J＝15.6Hz,1H),6.28(d,J＝10.9Hz,1H),2.50(q,J＝7.4Hz,2H),1.04(t,J＝7.4Hz,3H)；¹³C NMR(100MHz,CDCl₃)δ146.30,141.03,137.92,131.49,128.88,128.61,128.28,127.19,127.12,126.92,126.37,126.00,32.23,13.21；EI-MS m/z(％):234(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₈H₁₈[M]⁺:234.1409,found:234.1407.

Example 22

Synthesis of compound 3 cb:

starting from 1cb, the procedure is as in example 1, with a yield of 86%.

¹H NMR(400MHz,CDCl₃)δ7.37(t,J＝7.2Hz,2H),7.33–7.28(m,1H),7.22(dd,J＝6.2,2.6Hz,4H),7.20–7.16(m,2H),7.14(dt,J＝5.2,2.9Hz,1H),6.65(dd,J＝15.6,10.5Hz,1H),6.54(d,J＝15.6Hz,1H),6.26(d,J＝10.5Hz,1H),2.80–2.61(m,1H),1.09(d,J＝6.8Hz,6H)；¹³C NMR(100MHz,CDCl₃)δ151.11,141.09,137.93,131.39,129.23,128.58,128.11,127.17,127.15,126.95,126.35,124.62,36.14,22.00；EI-MS m/z(％):248(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₉H₂₀[M]⁺:248.1565,found:248.1560.

Example 23

Synthesis of compound 3 cc:

to a dry Schlenk tube, 3.4mg of Pd (OAc) was added under argon atmosphere₂，10.6mg P(2-OMe-Ph)₃63mg of 1cc (0.3mmol), 98mg of 2aa (0.6mmol), 141mg of CsOPiv, 3mL of THF, was heated to 110 ℃ and stirred for 3 hours. Quenching the reaction with 5mL of saturated ammonium chloride aqueous solution, extracting with 5mL of ethyl acetate three times, and dissolving the organic phase with saturated NaClWashing, drying with anhydrous sodium sulfate solid, concentrating, performing column chromatography with n-hexane as eluent, and collecting product band to obtain 3cc white solid 50.0mg with yield 72%.

¹H NMR(400MHz,CDCl₃)δ7.55–7.27(m,10H),7.20–7.07(m,2H),7.04–6.88(m,1H)；¹³C NMR(100MHz,CDCl₃)δ143.84,141.99,135.76,133.01,129.67,129.23,129.17,129.04,129.02,127.61,123.15,120.47,113.07；EI-MS m/z(％):231(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₇H₁₃N[M]⁺:231.1408,found:231.1045.

Example 24

Synthesis of compound 3 cd:

starting from 1cd, the procedure is as in example 23, with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.65(d,J＝11.3Hz,1H),7.46–7.37(m,3H),7.36–7.23(m,7H),6.97(d,J＝15.6Hz,1H),6.80(dd,J＝15.6,11.3Hz,1H),3.79(s,3H)；EI-MS m/z(％):264(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₈H₁₆O₂[M]⁺:264.1150,found:264.1157.

Example 25

Synthesis of Compound 3 da:

starting from 2da, the procedure is as in example 1, with a yield of 95%.

¹H NMR(400MHz,CDCl₃)δ7.45–7.34(m,3H),7.28(tt,J＝13.2,6.7Hz,7H),7.20(d,J＝8.1Hz,2H),7.07(d,J＝8.0Hz,2H),6.90–6.80(m,2H),6.71(dt,J＝11.3,7.1Hz,1H),2.31(s,3H)；¹³C NMR(100MHz,CDCl₃)δ142.67,142.53,140.01,137.59,134.86,134.06,130.80,129.43,128.60,128.35,128.34,127.71,127.55,127.48,126.53,126.33,21.40；EI-MS m/z(％):296(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₃H₂₀[M]⁺:296.1565,found:296.1566.

Example 26

Synthesis of Compound 3 db:

starting from 2db, the procedure is described in example 1, with a yield of 96%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.35(m,3H),7.33–7.17(m,11H),6.93–6.80(m,2H),6.72–6.62(m,1H)；¹³C NMR(100MHz,CDCl₃)δ143.89,142.28,139.79,136.14,133.11,132.55,130.73,128.86,128.42,128.39,128.06,127.79,127.76,127.74,127.71；EI-MS m/z(％):316(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈Cl[M+H]⁺:317.1092,found:317.1091.

Example 27

Synthesis of Compound 3 dc:

starting from 2dc, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.35(m,3H),7.32–7.23(m,9H),6.95(t,J＝8.7Hz,2H),6.88–6.75(m,2H),6.69(d,J＝14.6Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ162.36(d,J＝247.5Hz),143.33(d,J＝1.3Hz),142.36,139.88,133.83(d,J＝3.4Hz),132.69,130.74,128.41,128.38,128.18,128.10,128.02,127.72,127.65(d,J＝2.5Hz),126.98(d,J＝2.4Hz),115.67(d,J＝21.7Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-114.17；EI-MS m/z(％):300(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₂H₁₈F[M+H]⁺:301.1387,found:301.1388.

Example 28

Synthesis of Compound 3 dd:

starting from 2dd, the procedure is described in example 1 with a yield of 96%.

¹H NMR(400MHz,CDCl₃)δ7.50(d,J＝8.2Hz,2H),7.47–7.35(m,5H),7.29(ddd,J＝14.9,8.9,4.6Hz,7H),6.96(dd,J＝15.1,11.0Hz,1H),6.88(d,J＝11.0Hz,1H),6.74(d,J＝15.1Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ145.10,142.13,141.10,139.63,132.15,130.73,129.65,129.12(q,J＝32.3Hz),128.46,128.43,127.97,127.91,127.86,127.76,127.05(q,J＝270.4Hz),126.59,125.64(q,J＝3.8Hz)；¹⁹F NMR(376MHz,CDCl₃)δ-62.51；EI-MS m/z(％):350(M⁺)；HRMS(ESI):m/z Exact mass calcd for C₂₃H₁₇F₃[M]⁺:350.1277，found:350.1277.

Example 29

Synthesis of Compound 3 de:

starting from 2de, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.34(m,3H),7.27(ddd,J＝8.7,5.7,4.0Hz,9H),6.89–6.64(m,5H),3.79(s,3H)；¹³C NMR(100MHz,CDCl₃)δ159.34,142.56,142.07,140.07,133.64,130.80,130.47,128.67,128.36,128.33,127.85,127.64,127.49,127.39,125.26,114.17,55.43；EI-MS m/z(％):312(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₃H₂₀O[M]⁺:312.1514,found:312.1516.

Example 30

Synthesis of compound 3 df:

starting from 2df, the procedure is as in example 1, 73% yield.

¹H NMR(400MHz,CDCl₃)δ7.43–7.34(m,7H),7.32–7.22(m,8H),7.17(d,J＝11.4Hz,1H),6.47(d,J＝11.6Hz,1H),6.31(t,J＝11.4Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ145.22,142.45,139.76,137.76,131.24,130.76,129.27,128.47,128.34,128.27,128.02,127.73,127.69,127.23,124.40；EI-MS m/z(％):282(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₂H₁₈[M]⁺:282.1409,found:282.1406.

Example 31

Synthesis of compound 3 dg:

starting from 2dg, the procedure is as in example 23, giving a yield of 40%.

¹H NMR(400MHz,CDCl₃)δ7.42–7.32(m,3H),7.30–7.24(m,5H),7.23–7.19(m,2H),6.71(d,J＝11.0Hz,1H),6.44(dt,J＝16.8,10.5Hz,1H),5.39(dd,J＝16.8,1.7Hz,1H),5.13(dd,J＝10.1,1.7Hz,1H)；¹³C NMR(100MHz,CDCl₃)δ143.25,142.20,139.76,135.08,130.54,128.64,128.32,128.28,127.70,127.63,127.51,118.73；EI-MS m/z(％):206(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₆H₁₄[M]⁺:206.1096,found:206.1090.

Example 32

Synthesis of compound 3 dh:

starting from 2dh, the procedure is as in example 23, 83% yield.

¹H NMR(400MHz,CDCl₃)δ7.38(t,J＝7.2Hz,2H),7.32(t,J＝4.9Hz,1H),7.30–7.24(m,4H),7.24–7.18(m,3H),6.87(d,J＝11.4Hz,1H),5.92(d,J＝11.4Hz,1H),1.89(s,3H),1.76(s,3H)；¹³C NMR(100MHz,CDCl₃)δ143.23,140.32,139.82,137.90,130.71,128.25,128.23,127.56,127.14,127.03,124.63,123.28,26.65,18.78；EI-MS m/z(％):234(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₈H₁₈[M]⁺:234.1409,found:234.1402.

Example 33

Synthesis of Compound 3 di:

starting from 2di, the procedure is as in example 23, with a yield of 85%.

¹H NMR(400MHz,CDCl₃)δ7.36(dt,J＝24.3,7.1Hz,3H),7.30–7.18(m,7H),6.67(d,J＝11.0Hz,1H),6.14(dd,J＝15.1,10.9Hz,1H),5.96–5.84(m,1H),2.04(dd,J＝14.1,7.0Hz,2H),1.39(dq,J＝14.7,7.4Hz,2H),0.89(t,J＝7.4Hz,3H)；¹³C NMR(100MHz,CDCl₃)δ142.70,140.28,140.17,137.30,130.63,128.56,128.55,128.27,128.25,127.52,127.23,127.14,35.23,22.72,13.87；

Example 34

Synthesis of compound 3 dj:

starting from 2dj, the procedure is as in example 23, with a yield of 49%.

¹H NMR(400MHz,CDCl₃)δ7.33(d,J＝4.7Hz,3H),7.29–7.22(m,4H),7.22–7.16(m,3H),6.88(s,1H),5.86(s,1H),2.29(s,2H),1.77(d,J＝5.2Hz,2H),1.69(dt,J＝13.8,7.0Hz,2H)；¹³C NMR(101MHz,CDCl₃)δ143.18,142.83,140.98,140.00,135.50,130.72,128.21,127.81,127.27,127.23,127.05,125.42,33.55,32.22,24.44；EI-MS m/z(％):246(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₉H₁₈[M]⁺:246.1409,found:246.1414.

Example 35

Synthesis of compound 3 dk:

starting from 2dk, the procedure is as in example 23, 53% yield.

¹H NMR(400MHz,CDCl₃)δ7.35–7.28(m,3H),7.28–7.17(m,7H),6.55(s,1H),5.85–5.76(m,1H),2.14–2.06(m,2H),1.70–1.60(m,2H),1.52–1.46(m,2H),1.45–1.39(m,2H)；¹³C NMR(101MHz,cdcl₃)δ144.08,141.44,138.66,136.53,132.38,132.27,130.64,128.14,127.91,127.51,127.06,126.89,28.25,26.36,23.10,22.19；EI-MS m/z(％):260(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₀H₂₀[M]⁺:260.1565,found:260.1555.

Example 36

Synthesis of Compound 3 dl:

starting from 2dl, see example 23 for an operation with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.32(m,3H),7.31–6.98(m,7H),6.56(s,1H),5.76(s,1H),4.21(d,J＝1.7Hz,2H),3.56(t,J＝5.3Hz,2H),1.74(s,2H)；¹³C NMR(101MHz,cdcl₃)δ143.42,140.80,140.30,134.10,130.54,130.00,129.15,128.23,128.11,127.52,127.46,127.31,66.13,64.38,28.43；EI-MS m/z(％):262(M⁺)；HRMS(EI):m/z Exact mass calcd for C₁₉H₁₈O[M]⁺:262.1358,found:262.1351.

Example 37

Synthesis of Compound 3 dm:

starting from 2dm, the procedure is described in example 23 with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.44–7.34(m,4H),7.34–7.27(m,5H),7.24–7.18(m,2H),6.79(d,J＝11.5Hz,1H),6.05(dd,J＝15.2,0.5Hz,1H),4.17(q,J＝7.1Hz,2H),1.26(t,J＝7.1Hz,3H)；EI-MS m/z(％):278(M⁺).

Example 38

Synthesis of compound 3 do:

starting from 2do, the procedure is described in example 1, with a yield of 81%.

¹H NMR(400MHz,CDCl₃)δ7.32–7.25(m,5H),7.16–7.06(m,10H),7.05–7.00(m,3H),6.82–6.75(m,3H),6.53(s,1H)；¹³C NMR(100MHz,CDCl₃)δ143.64,143.46,140.21,139.75,137.29,132.82,131.81,130.49,129.62,129.39,128.27,128.25,127.97,127.96,127.90,127.57,126.98,126.91,126.72；EI-MS m/z(％):358(M⁺)；HRMS(EI):m/z Exact mass calcd for C₂₈H₂₂[M]⁺:358.1722,found:358.1720.

Example 39

Examination of p-styryl borate ester:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(2.5mol％)，P(2-OMe-Ph)₃(5 mol%), 1aa (0.3mmol), styryl borate (0.6mmol) (shown in the following Table [ B ]]) CsOPiv (0.6mmol), 3mL THF, warmed to 110 deg.CAnd stirring for 3 hours. Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. Different styryl borate ester researches are carried out, and the specific conditions and effects are as follows:

in No. 3, the styrylboronic acid pinacol ester had superior yield and migration ratio.

Example 40

Examination of boron ester equivalent and reaction temperature:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(2.5mol％)，P(2-OMe-Ph)₃(5 mol%), 1aa (0.3mmol), styryl borate 2aa (equivalent eq as shown in the following table), CsOPiv (0.6mmol), 3mL THF, and stirred for 3h at elevated temperature (as shown in the following table). Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. The research on the equivalent weight and the reaction temperature of different boron esters is carried out, and the specific conditions and effects are as follows:

from the above, the yield is better when the reaction temperature is 70 ℃; when the styryl boronic acid pinacol ester is 2 to 3 equivalents, the yield is excellent.

EXAMPLE 41

Investigation of the ligands:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(2.5 mol%), ligand L (shown in the following Table), 1aa (0.3mmol), styrylboronic acid ester (0.6mmol), CsOPiv (0.6mmol), 3mL THF, warmed to 70 ℃ and stirred for 3 h. Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4.

The study of different ligands was carried out under the following conditions and effects:

as can be seen from the above, ligand P (2-OMe-Ph)₃The effect of (2) is better.

Example 42

Investigation of the base:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(2.5mol％)，P(2-OMe-Ph)₃(5 mol%), 1aa (0.3mmol), styrylboronic acid 2aa (0.6mmol), a base (shown in the following table) (0.6mmol), 3mL of THF, warming to 70 ℃ and stirring for 3 h. Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. The research of different alkalis is carried out, the specific conditions andthe effects are as follows:

from the above, it is found that the effect of the alkali being an organic acid salt of an alkali metal salt is excellent, and cesium pivalate is particularly preferable.

Example 43

Investigation of reaction solvent:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(2.5mol％)，P(2-OMe-Ph)₃(5 mol%), 1aa (0.3mmol), styrylboronic acid ester 2aa (0.6mmol), CsOPiv (0.6mmol), and 3mL of a solvent (shown in the following Table), the temperature was raised to 70 ℃ and the mixture was stirred for 3 hours. Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. Different solvents were studied, and the specific conditions and effects are as follows:

from the above, in most organic solvents, superior effects can be obtained; especially, tetrahydrofuran has better effect.

Example 44

Investigation of the catalyst:

in a dry Schlenk tube, under argon, the catalyst (shown in the table below) (2.5 mol%), P (2-OMe-Ph) was added separately₃(5 mol%), 1aa (0.3mmol), styrylboronic acidEster 2aa (0.6mmol), CsOPiv (0.6mmol), 3mL THF solvent, warm to 70 deg.C, stir for 3 h. Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. Different catalysts were studied, and the specific conditions and effects are as follows:

from the above, the effect of the palladium source catalyst is often excellent.

Example 45

Investigation of reaction time and catalyst equivalent:

in a dry Schlenk tube, under the protection of argon, Pd (OAc) was added₂(mol% as shown in the following Table), P (2-OMe-Ph)₃(5 mol%), 1aa (0.3mmol), styrylboronic acid 2aa (0.6mmol), CsOPiv (0.6mmol), 3mL THF solvent, and heated to 70 ℃ with stirring for a certain period of time (as shown in the following Table). Quenching the reaction by using 5mL of saturated ammonium chloride aqueous solution, extracting the reaction product by using 5mL of ethyl acetate for three times, washing an organic phase by using a saturated NaCl solution, drying an anhydrous sodium sulfate solid, concentrating the solid, performing column chromatography by using normal hexane as an eluent, and collecting a product band to obtain 3aa and a compound 4. The studies of different reaction times and different catalyst equivalents were carried out, and the specific conditions and effects are as follows:

from the above, the catalyst can obtain better effect and has fast reaction conversion rate under the conventional catalyst dosage in the field.

Example 46

Examination of aryl iodide reactivity:

the procedure is described in example 1, with a yield of 70% and the product data in example 12, starting from aryl iodide.

Study on reaction and product stereoselectivity

1) Cis-trans selectivity of the double bond in position 1

Compound 3ae (example 5)¹In H NMR, there are two characteristic hydrogens at δ ═ 7.15 to 7.08(m,2H), respectively, while compound 3df has no characteristic peak at this point.

Compound 3bd (example 13)¹In H NMR, there are two characteristic hydrogens at δ ═ 7.03 to 6.91(m,2H), respectively, while compound 3ae has no characteristic peak here.

Comparison of nuclear magnetic data for compound 3ae (example 5) and compound 3bd (example 13) allows determination of the cis-trans selectivity of the double bond at position 1.

2) Cis-trans selectivity of the double bond in position 3

Compound 3aa (example 1)¹In H NMR, there are three characteristic hydrogens at δ 6.95-6.83 (m,2H),6.74(dt, J10.8, 7.4Hz,1H), respectively, while compound 3df has no characteristic peak here.

Compound 3df (example 30)¹In H NMR, δ is 7.17(d, J is 11.4Hz,1H),6.47(d, J is 11.6Hz,1H),6.31(t, J is 11.4Hz,1H), respectively, with three characteristic hydrogens, while compound 3aa has no characteristic peak here.

Comparison of nuclear magnetic data for compound 3aa (example 1) and compound 3df (example 30) allows determination of the cis-trans selectivity of the double bond at position 3.

3) Compound 3ba (example 10)

The single crystal structure of (a) shows that both double bonds are of a single configuration, i.e. (E, E).

As mentioned above, during the 1,4-Pd migration/Suzuki reaction, the following reaction pathway exists: 1) because the alkenyl boron reagent is used as a high-activity transmetallization reagent, the transmetallization speed is high, and the non-migrated Suzuki reaction product or the high non-migrated Suzuki reaction product can be directly obtained without 1,4-Pd migration;

2) due to the existence of the following 1,5-Pd migration pathway, it is difficult to obtain a single cis-or trans-isomer;

3) during the reaction, e.g. under basic or light conditions, Z/E of the double bond may be isomerized, and the desired single cis-or trans-isomer product may still not be obtained.

Therefore, it is technically difficult and almost impossible to obtain a single cis-or trans-isomer product of a 1, 3-conjugated diene compound having a high migration ratio with high stereoselectivity in a mechanistic analysis as a whole.

The single crystal structure and nuclear magnetic comparison analysis show that the preparation method provided by the invention can obtain a product with stereoselectivity and configuration unicity, and the condition that the existing Heck reaction obtains a Z/E mixed product does not exist, so that unexpected technical effects are obtained.

Example 47

Measurement of optical Properties of partially differentiated Compounds

(1) Preparation of compound A-D mother liquor:

weighing 0.01mmol of compound, dissolving in 1mL of chromatographic pure THF, and mixing well by ultrasonic oscillation to obtain 10^-2mmol solution; taking 100uL of the above solution by a pipette, adding 900uL of chromatographic pure THF for dissolving, and performing ultrasonic oscillation to obtain 10^-3mmol solution; taking 40uL of the solution by using a pipette, adding 3mL of chromatographic pure THF (tetrahydrofuran) +960uL of the solution for dissolving, and carrying out ultrasonic oscillation to prepare the 10^{- 5}mmol of the solution.

(2) Determination of maximum absorption wavelength of Compounds A to D

2mL of the above solution was taken and tested for the maximum absorption peak of each compound in a UV/Vis spectrometer.

(3) Measurement of Absolute Quantum efficiency of Compounds A to D (solution State)

Taking 2mL of the solution, testing the solution in an absolute quantum efficiency tester, setting the excitation wavelength as the maximum absorption wavelength of each compound, and measuring the absolute quantum efficiency.

(4) Measurement of Absolute Quantum efficiency of Compounds A to D (solid State)

2mg of the compound is taken and tested in an absolute quantum efficiency tester, the excitation wavelength is set as the maximum absorption wavelength of each compound, and the absolute quantum efficiency is measured.

From the above, it is understood that compound A, B, C, D has Aggregation Induced Emission (AIE) effect, i.e., no light is emitted in the solution state and light is emitted in the solid state. Comparing compound a and compound B, the carbon-carbon double bond at position 3 has an effect on the aggregation state luminescence quantum efficiency, and the aggregation state quantum efficiency of the E-type double bond is greater than that of the Z-type double bond (compound a ═ 23.0%, compound B ═ 3.1%). Comparing compound C and compound D, the carbon-carbon double bond at position 1 has an effect on the aggregation state luminescence quantum efficiency, and the aggregation state quantum efficiency of the E-type double bond is greater than that of the Z-type double bond (compound C ═ 12.0%, compound B ═ 41.5%).

Claims (11)

1. A process for producing a 1, 3-conjugated diene compound, characterized by comprising the steps of: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand and an alkaline reagent, carrying out 1,4-Pd migration/suzuki coupling reaction shown in the specification on an aromatic halide containing a structural fragment shown in a formula I and an alkenyl boron compound containing a structural fragment shown in a formula II to obtain a compound containing a structural fragment of 1, 3-conjugated diene shown in a formula III;

wherein X is bromine or iodine;

[B]is composed of

R^aAnd R^bIndependently is H or C₁-C₆Alkyl, or, R^aAnd R^bIs connected with

Together form an unsubstituted or substituted 5-to 6-membered heterocycloalkyl; said substitution means substitution with one or more of the following substituents: c₁～C₆Alkyl or phenyl; when the number of the substituents is plural, the substituents may be the same or different;

the aromatic halide containing the structural fragment shown in the formula I is shown in the formula I ', the alkenyl boron compound containing the structural fragment shown in the formula II is shown in the formula II', and the compound containing the structural fragment of the 1, 3-conjugated diene shown in the formula III is correspondingly obtained;

wherein the content of the first and second substances,

is optionally substituted C₆-C₁₀Aryl or optionally substituted 5-to 6-membered heteroaryl; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-3;

R²、R³、R⁴and R⁵Independently is H, -CN, -NO₂、-C(＝O)-R^2-1、-C(＝O)-N(R^2-2R^2-3) Optionally substituted C₁-C₆Alkyl, optionally substituted C₃-C₁₀Cycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkenyl, optionally substituted C₆-C₁₀Aryl, or, optionally substituted 5-6 membered heteroaryl; said C₃～C₁₀In the heterocycloalkyl group (b), the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-4; said C₃～C₁₀In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 4; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-4;

or, R³And R⁴Or, R³And R⁵Together with the carbon to which it is directly attached form optionally substituted C₄～C₆Or optionally substituted C₃～C₅The heterocycloalkenyl group of (a); said C₃～C₅In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 2;

said R³And R⁴Or, R³And R⁵Together with the carbon to which it is directly attached form optionally substituted C₄～C₆Or optionally substituted C₃～C₅The heterocycloalkenyl of (1), the

In (1) optionally substituted C₆-C₁₀Aryl or optionally substituted 5-to 6-membered heteroaryl, and said R²、R³、R⁴And R⁵In (1) optionally substituted C₁-C₆Alkyl, optionally substituted C₃-C₁₀Cycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkyl, optionally substituted C₃-C₁₀Heterocycloalkenyl, optionally substituted C₆-C₁₀In aryl or optionally substituted 5-6 membered heteroaryl, the optional substitutions are each independently unsubstituted or substituted with one or more of the following substituents whenWhen plural, the substituents are the same or different: H. f, Cl, -NO₂、-OH、-CN、-N(R^1-1R^{1 -2})、-C(＝O)-R^1-3、-O-C(＝O)-R^1-4、-N(R^1-5)-C(＝O)-R^1-6、-C(＝O)-N(R^1-7R^1-8)、-O-C(＝O)-N(R^1-9R^1-10)、-S(＝O)-N(R^1-11R^1-12)、-S(＝O)₂-N(R^1-13R^1-14) Unsubstituted or substituted C₁～C₆Alkyl, unsubstituted or substituted C₁～C₆alkyl-O-, unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, unsubstituted or substituted C₃-C₆Cycloalkyl, unsubstituted or substituted C₃-C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkenyl, unsubstituted or substituted C₆-C₁₀Aryl, or unsubstituted or substituted 5-to 6-membered heteroaryl; said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-4; said C₃～C₅In the heterocycloalkenyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-4; said substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In the aryl or the substituted 5-6-membered heteroaryl, the substitution is independently one or more of the following substituents, and when the substituents are multiple, the substituents are the same or different: F. cl, -NO₂、-OH、-CN、-C(＝O)H、-COOH、-NH₂、-C(＝O)NH₂、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O;

R^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^1-12、R^1-13and R^1-14Independently is H, unsubstituted or substituted C₁～C₆Alkyl, unsubstituted or substituted C₁～C₆alkyl-O-, unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, unsubstituted or substituted C₃～C₆Cycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅Heterocycloalkenyl, unsubstituted or substituted phenyl, or unsubstituted or substituted 5-to 6-membered heteroaryl; said C₃～C₅In the heterocycloalkyl group, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3; said C₃～C₅In the heterocycloalkenyl group (b), the hetero atom is one or more of oxygen, sulfur and nitrogen, and the number of the hetero atoms is 1 to 3; in the 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-3; said substituted C₁～C₆Alkyl, said substituted C₁～C₆alkyl-O-, said substituted C₂～C₆Alkenyl, said substituted C₂～C₆alkenyl-O-, said substituted C₃～C₆Cycloalkyl, said substituted C₃～C₅Heterocycloalkyl, said substituted C₃～C₅In heterocycloalkenyl, the substituted phenyl, or the substituted 5-to 6-membered heteroaryl, the substitutions each independently refer to one or more of the following substituents: F. cl, -OH, -CF₃、-CN、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O; when the number of the substituents is plural, the substituents are the same orDifferent;

or, R^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅Heterocycloalkyl, unsubstituted or substituted C₃～C₅The heterocycloalkenyl group of (a), or the unsubstituted or substituted 5-to 6-membered heteroaryl group; said C₃～C₅In the heterocyclic alkyl, the heteroatom is nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-3; said C₃～C₅In the heterocycloalkenyl, the heteroatoms are nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-3; in the 5-6-membered heteroaryl, the heteroatoms are nitrogen, or nitrogen, oxygen and/or sulfur, and the number of the heteroatoms is 1-3; said substituted C₃～C₅Of (a) heterocycloalkyl, said substituted C₃～C₅In the heterocycloalkenyl group or the substituted 5-to 6-membered heteroaryl group, the substitution is independently one or more of the following substituents: F. cl, -OH, -CF₃、-CN、C₁～C₆Alkyl radical, C₁～C₆alkyl-O-or ═ O; when the substituent is plural, the substituents may be the same or different.

2. The preparation method according to claim 1, wherein the organic solvent is one or more of an ether solvent, a halogenated hydrocarbon solvent, an amide solvent, an aromatic hydrocarbon solvent, an alcohol solvent and an alkane solvent;

and/or the palladium catalyst is one or more of tris (dibenzylideneacetone) dipalladium-chloroform adduct, palladium chloride, palladium acetate, tetratriphenylphosphine palladium, dichlorotriphenylphosphine palladium and dichlorodiphenylnitrile palladium;

and/or the phosphine ligand is tris (2-methoxyphenyl) phosphine, triphenylphosphine, tris (4-methyl-phenyl) phosphine, tris (4-methoxy-phenyl) phosphine, tris (3-methoxy-phenyl) phosphine, tris (2, 6-dimethoxy-phenyl) phosphine, tris (2,4, 6-trimethoxy-phenyl) phosphine, tricyclohexylphosphine, tri-tert-butylphosphine tetrafluoroborate, benzyldiphenylphosphine, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 6-bis (diphenylphosphino) hexane, 9-dimethyl-4, one or more of 5-bis diphenylphosphinoxaanthracene, 4, 5-bis (di-t-butylphosphino) -9, 9-dimethylxanthene, 4, 6-bis (diphenylphosphino) phenazine, 3- (dicyclohexylphosphino) -1-methyl-2-phenyl-1H-indole, bis (2-diphenylphosphino) ether, 1, 2-bis (diphenylphosphino) benzene, 1' -bis (diphenylphosphino) ferrocene, and R- (+) -2,2' -bis (diphenylphosphino) -1,1' -binaphthyl;

and/or, the alkaline reagent is one or more of alkali metal salt, alkali metal hydroxide and organic base;

and/or the molar volume ratio of the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I to the organic solvent is 0.05 mmol/mL-1 mmol/mL;

and/or the molar ratio of the alkenyl boron compound shown in the formula II to the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I is 1: 1-5: 1;

and/or the molar percentage of the palladium catalyst and the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I is 2.5-10 mol%;

and/or the molar ratio of the ligand to the palladium catalyst is 1: 1-2: 1;

and/or the molar ratio of the alkaline reagent to the aromatic halide substituted by the double bond at the ortho position on the aromatic ring shown in the formula I is 1: 1-5: 1;

and/or the reaction temperature is 50-120 ℃;

and/or the reaction is carried out in an inert atmosphere.

3. The method according to claim 2, wherein when the organic solvent is an ether solvent, the ether solvent is one or more of tetrahydrofuran, dioxane, diethyl ether, 2-methyl-tetrahydrofuran, methyl tert-butyl ether and ethylene glycol dimethyl ether;

and/or, when the organic solvent is a halogenated hydrocarbon solvent, the halogenated hydrocarbon solvent is dichloromethane;

and/or, when the organic solvent is an amide solvent, the amide solvent is N, N-dimethylformamide;

and/or, when the organic solvent is an aromatic solvent, the aromatic solvent is toluene;

and/or, when the organic solvent is an alcohol solvent, the alcohol solvent is n-butanol;

and/or, when the organic solvent is an alkane solvent, the alkane solvent is n-hexane;

and/or, the palladium catalyst is palladium acetate;

and/or the phosphine ligand is tri (2-methoxyphenyl) phosphine;

and/or, when the alkaline agent is an alkali metal salt, the alkali metal salt is one or more of cesium acetate, cesium fluoride, cesium carbonate, cesium pivalate, cesium trifluoroacetate, potassium fluoride and potassium phosphate;

and/or, when the alkaline agent is an alkali metal hydroxide, the alkali metal hydroxide is potassium hydroxide;

and/or, when the alkaline reagent is an organic base, the organic base is triethylamine;

and/or the molar volume ratio of the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I to the organic solvent is 0.3 mmol/mL;

and/or the molar ratio of the alkenyl boron compound shown in the formula II to the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I is 2: 1-3: 1;

and/or the molar percentage of the palladium catalyst and the aromatic halide substituted by the ortho-position double bond on the aromatic ring shown in the formula I is 5 mol%;

and/or the molar ratio of the alkaline reagent to the aromatic halide substituted by the double bond at the ortho position on the aromatic ring shown in the formula I is 2: 1-3: 1;

and/or the reaction temperature is 70-110 ℃;

and/or when the reaction is carried out in an inert atmosphere, the inert atmosphere is nitrogen and/or argon.

4. The method of claim 1, wherein when R is^aOr R^bIs C₁-C₆When alkyl, said C₁-C₆Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;

and/or when R^aAnd R^bIs connected with

When taken together form an unsubstituted or substituted 5-to 6-membered heterocycloalkyl group, the 5-to 6-membered heterocycloalkyl group is

And/or when R^aAnd R^bIs connected with

Together form a substituted 5-to 6-membered heterocycloalkyl, said substitution being C₁-C₆When alkyl, said C₁-C₆Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;

and/or when R^aAnd R^bIs connected with

Together form a substituted 5-6 membered heterocycloalkyl, which when substituted is phenyl, is cycloconnected to the 5-6 membered heterocycloalkyl;

and/or when R^aAnd R^bIs connected with

Together form a substituted 5-to 6-membered heterocycloalkyl group, the number of substitutions being 1,2,3 or 4.

5. The process according to claim 4, wherein [ B ] is]Is composed of

When it is used, the

Is any one of the following structures:

6. the method according to any one of claims 1 to 5, wherein the method is carried out while the

Is optionally substituted C₆-C₁₀When aryl, said C₆-C₁₀Aryl is phenyl;

and/or, when said

When the aryl group is an optionally substituted 5-6-membered heteroaryl group, the 5-6-membered heteroaryl group contains 2-5 carbon atoms, and one or more of N, O heteroatoms and S, and the number of the heteroatoms is 1-3;

and/or, when said

Is optionally substituted C₆-C₁₀In aryl or optionally substituted 5-6 membered heteroaryl, the number of substitutions is 1,2,3 or 4;

and/or, when said

Is optionally substituted C₆-C₁₀In aryl or optionally substituted 5-6 membered heteroaryl, the substituted position is alpha, beta, gamma or delta of X;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₁-C₆When alkyl, said C₁～C₆Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When there is a cycloalkyl group, said C₃-C₁₀Cycloalkyl being C₃-C₆A cycloalkyl group;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When it is heterocycloalkyl, said C₃-C₁₀Heterocycloalkyl being C₃-C₅Heterocycloalkyl radical of said formula C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When it is heterocyclenyl, said C₃-C₁₀Heterocycloalkenyl is C₃-C₅Heterocycloalkenyl group of said C₃-C₅In the heterocycloalkenyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₆-C₁₀When aryl, said optionally substituted C₆-C₁₀Aryl is phenyl or naphthyl;

and/or whenSaid R²、R³、R⁴Or R⁵When the aryl is an optionally substituted 5-6-membered heteroaryl, in the optionally substituted 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-2;

and/or, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₄～C₆Cycloalkenyl of (a), C₄～C₆The cycloalkenyl group of (a) is cyclopentenyl or cyclohexenyl;

and/or, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₃～C₅When said heterocycloalkenyl group is (a), said C₃～C₅The heterocycloalkenyl group of (a) is a 2H-pyranyl group;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₂～C₆Alkenyl, or unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is ethenyl, propenyl, or butenyl;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₃-C₆When there is a cycloalkyl group, said C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₃-C₅When it is heterocycloalkyl, said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said optionally substituted substituent is notSubstituted or substituted C₃-C₅When it is heterocyclenyl, said C₃-C₅In the heterocycloalkenyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₆-C₁₀When aryl, said optionally substituted C₆-C₁₀Aryl is phenyl or naphthyl;

and/or, when the substituent in the optional substitution is unsubstituted or substituted 5-6-membered heteroaryl, in the optionally substituted 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-2;

and/or, when said substituent in said optional substitution is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In aryl or substituted 5-6 membered heteroaryl, the substitution is C₁～C₆Alkyl or C₁～C₆alkyl-O-said C₁～C₆Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;

and/or, when said substituent in said optional substitution is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃-C₆Cycloalkyl, substituted C₃-C₅Heterocycloalkyl, substituted C₃～C₅Heterocycloalkenyl, substituted C₆-C₁₀In the aryl or the substituted 5-6-membered heteroaryl, the number of the substitution is 1,2,3 or 4;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is ethenyl, propenyl, or butenyl;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₃～C₆When there is a cycloalkyl group, said C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₃-C₅When it is heterocycloalkyl, said C₃-C₅In the heterocyclic alkyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₃-C₅When it is heterocyclenyl, said C₃-C₅In the heterocycloalkenyl, the heteroatom is one or more of oxygen, sulfur and nitrogen, and the number of the heteroatoms is 1-3;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14When the aryl is unsubstituted or substituted 5-6-membered heteroaryl, in the optionally substituted 5-6-membered heteroaryl, the number of heteroatoms is one or more of N, O and S, and the number of heteroatoms is 1-2;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃～C₆Cycloalkyl, substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅In the heterocycloalkenyl group, the substituted phenyl group or the substituted 5-to 6-membered heteroaryl group, the substitution is C₁～C₆Alkyl or C₁～C₆alkyl-O-said C₁～C₆Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is substituted C₁～C₆Alkyl, substituted C₁～C₆alkyl-O-, substituted C₂～C₆Alkenyl, substituted C₂～C₆alkenyl-O-, substituted C₃～C₆Cycloalkyl, substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅When the heterocyclic alkenyl group, the substituted phenyl group or the substituted 5-6-membered heteroaryl group is adopted, the number of the substitution is 1,2,3 or 4;

and/or, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅When said heterocycloalkyl group is (C)₃～C₅In the heterocyclic alkyl, the heteroatom is nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-2;

and/or, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently together with the nitrogen to which it is directly attached form unsubstituted or substituted C₃～C₅When said heterocycloalkenyl group is (a), said C₃～C₅In the heterocycloalkenyl, the heteroatoms are nitrogen, or nitrogen and oxygen and/or sulfur, and the number of the heteroatoms is 1-2;

and/or, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14When the nitrogen atoms are respectively and independently combined with the directly connected nitrogen to form unsubstituted or substituted 5-6-membered heteroaryl, in the 5-6-membered heteroaryl, the heteroatoms are nitrogen, or nitrogen, oxygen and/or sulfur, and the number of the heteroatoms is 1-2;

and/or, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently taken together with the nitrogen to which it is directly attached form substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅The heterocycloalkenyl or substituted 5-to 6-membered heteroaryl of (a) wherein the substitution is C₁～C₆Alkyl or C₁～C₆C as described for alkyl-O-, said substitution₁～C₆Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;

and/or, when said R is^2-2And R^2-3、R^1-1And R^1-2、R^1-7And R^1-8、R^1-9And R^1-10、R^1-11And R^1-12Or, R^1-13And R^1-14Each independently taken together with the nitrogen to which it is directly attached form substituted C₃～C₅Heterocycloalkyl, substituted C₃～C₅When the heterocycloalkenyl group or the substituted 5-to 6-membered heteroaryl group is mentioned, the number of the substitutions is 1,2,3 or 4 independently of each other.

7. As claimed in claimThe process according to claim 6, wherein R is²、R³、R⁴Or R⁵Is optionally substituted C₁-C₆When alkyl, said C₁～C₆Alkyl is methyl, ethyl or n-propyl;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₃-C₁₀When there is a cycloalkyl group, said C₃-C₁₀Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

and/or, when said R is²、R³、R⁴Or R⁵Is optionally substituted C₆-C₁₀Aryl, said optionally substituted C₆-C₁₀When aryl is naphthyl, said naphthyl is

And/or, when said R is²、R³、R⁴Or R⁵When the aryl is an optionally substituted 5-6 membered heteroaryl, the optionally substituted 5-6 membered heteroaryl is thienyl;

and/or, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₄～C₆Cycloalkenyl of (a), C₄～C₆Cycloalkenyl of

And/or, when said R is³And R⁵Together with the carbon-carbon double bond directly attached to form optionally substituted C₃～C₅When said heterocycloalkenyl group is (a), said C₃～C₅The heterocyclic alkenyl group of is

And/or, when said optionally substituted substituents are unsubstituted or substitutedSubstituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl is methyl;

and/or, when said optionally substituted substituent is unsubstituted or substituted C₂～C₆Alkenyl, or unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is ethenyl, 1-propenyl, 2-butenyl, 1-butenyl or butadiene;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₁～C₆Alkyl, or, unsubstituted or substituted C₁～C₆alkyl-O-said C₁～C₆Alkyl is independently methyl or ethyl;

and/or, when said R is^2-1、R^2-2、R^2-3、R^1-1、R^1-2、R^1-3、R^1-4、R^1-5、R^1-6、R^1-7、R^1-8、R^1-9、R^1-10、R^1-11、R^{1 -12}、R^1-13Or R^1-14Is unsubstituted or substituted C₂～C₆Alkenyl, unsubstituted or substituted C₂～C₆alkenyl-O-, said C₂～C₆Alkenyl is ethenyl, 1-propenyl or 2-propenyl, 2-butenyl, 1-butenyl or butadiene.

8. The method of claim 7, wherein the step of preparing the composition is carried out in the presence of a catalyst

Is composed of

And/or, R²、R³、R⁴Or R⁵Is H, -CN, methyl, ethyl, isopropyl, n-propyl, -C (═ O) -O-CH₃、-C(＝O)-O-C₂H₅、

9. The method of claim 8, wherein the aromatic halide represented by formula I' comprising the structural fragment represented by formula I is any one of the following compounds:

and/or the alkenyl boron compound containing the structural fragment shown in the formula II' is any one of the following compounds:

and/or the compound containing the structural fragment of the 1, 3-conjugated diene shown in the formula III' is any one of the following compounds:

10. an application of 1, 3-butadiene compound shown in formula X as organic electroluminescent material,

the 1, 3-butadiene compound shown in the formula X is characterized in that the structure of the 1, 3-butadiene compound is shown as any one of the following compounds:

11. a1, 3-butadiene compound represented by the formula X',

the 1, 3-butadiene compound shown in the formula X' is characterized in that the structure of the 1, 3-butadiene compound is shown as any one of the following compounds:

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