Cinchona alkaloid-derived tetrazole tridentate chiral n,n,p-ligand, and preparation method therefor and use thereof

Abstract

The present invention relates to the field of organic chemical ligands. Disclosed are a cinchona alkaloid-derived tetrazole tridentate chiral N,N,P-ligand having a structure of general formula I (Zhang Yu-Feng type chiral anionic ligand) and a method for synthesizing the ligand. In the present invention, developed is a class of structurally novel tridentate N,N,P-ligands using a cinchona alkaloid tetrazole derivative and a highly sterically hindered trivalent phosphorus as a core scaffold (such scaffold ligands are referred to as Zhang Yu-Feng type chiral anionic ligands). Such novel chiral ligands have abundant structural characteristics. The electronic and steric hindrance effects of aryl substituents on the trivalent phosphorus can be regulated. In addition, additional weak interactions can be provided by means of an alkyl chain, thereby inducing excellent enantioselectivity. The ligand of the present invention can be widely applied to stereoconvergent radical asymmetric cross-coupling reactions of secondary dialkyl-substituted haloalkanes and sulfinimines, and has important guiding significance for the development of novel catalytic systems to enable other types of stereoconvergent radical asymmetric reactions.

Description

A cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand (Zhang Yufeng type chiral anionic ligand), its preparation method and uses Technical Field

[0001] This invention belongs to the field of chiral ligands in organic chemistry, specifically a cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P- ligand (Zhang Yufeng type chiral anionic ligand) and its preparation method and uses. Background Technology

[0002] Quinine and its analogues are important chiral natural products widely found in nature. Due to their complex spatial structures and multiple coordination sites, they have long been used in asymmetric catalytic reactions of small organic molecules. In recent years, with the rapid development of inexpensive 3d transition metal asymmetric catalysis, the demand for various novel chiral ligand frameworks has increased. Quinine and its analogue-derived N,N,P chiral anionic ligands contain a tertiary amine, a trivalent phosphorus, and an amide structure (which can be deprotonated under the action of a base to generate an amide anion). The tertiary amine and trivalent phosphorus can form coordinate bonds with the metal, and the amide nitrogen, after deprotonation by a base, can form an ionic bond with the metal, forming an electron-rich chiral complex with a metal center for catalytic reactions. This type of anionic ligand can enhance the reducing power of transition metals, enabling them to undergo single-electron transfer reactions with haloalkanes to generate alkyl radical species; it can also solve the problem of transition metal poisoning, thus addressing some problems that neutral ligands cannot solve. Therefore, the design and synthesis of novel anionic ligands has become a research hotspot in the field of metal asymmetric catalysis.

[0003] With the increasing attention paid to transition metal-catalyzed radical asymmetric chemistry, novel metal and chiral ligand skeletons have become research hotspots. Previously, quinine-derived nitrogen-phosphorus ligands have been reported for copper-catalyzed radical asymmetric coupling chemistry at activation sites such as the β-, propyl-, allylic, amide α-, ketone α-, and cyano α-. However, the previously synthesized ligands, with their commercially available aryl or alkyl substituents on the phosphorus, have structural limitations, particularly regarding poor asymmetric catalytic performance for secondary alkyl radical intermediates at non-activated sites. The dialkyl prochiral substrates exhibit low distinguishability, making them difficult to differentiate effectively in conventional catalytic systems, resulting in low stereoselectivity and low optical purity of the products. The asymmetric catalytic construction of chiral compounds involving these compounds is a significant challenge in organic chemistry, requiring further development of more types of chiral anionic ligands to provide specific stereoenvironments for such reactions, thereby achieving broader-spectrum asymmetric catalytic systems.

[0004] Therefore, further modification of the ligand skeleton structure of cinchona alkaloids to obtain novel cinchona alkaloid compounds is of great application value for enriching the types of catalysts and expanding their application range. Summary of the Invention

[0005] The purpose of this invention is to provide a widely applicable and novel tridentate N,N,P-chiral anionic ligand (Chinese name: ZhangYu-Feng type chiral anionic ligands, English name: ZhangCAL).

[0006] The first aspect of this invention provides a compound selected from: tetrazolium tridentate chiral N,N,P-ligand compounds derived from cinchona alkaloids of general formula I, or their tautomers, enantiomers, or diastereomers:

[0007] Wherein, the R 1 Selected from substituted or unsubstituted alkyl groups;

[0008] The R 2 Each is independently selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted monocyclic aryl groups, and C6-C14 substituted or unsubstituted fused ring groups;

[0009] The R 3 Selected from alkoxy groups;

[0010] The carbon atom marked with * is an R configuration, an S configuration, or an achiral carbon atom.

[0011] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, a plurality of the R... 2 Each of the fused ring groups is independently selected from C6 to C14, wherein the fused ring group is formed by the fusion of at least one first ring and at least one second ring, wherein the first ring is selected from C3 to C6 cycloalkyl and the second ring is selected from monocyclic aryl.

[0012] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, a plurality of the R... 2 Each is independently selected from substituted or unsubstituted naphthalene rings, substituted or unsubstituted anthracene rings, and substituted or unsubstituted phenanthrene rings.

[0013] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, a plurality of the R... 2 Each is independently selected from a monocyclic aryl group, wherein any hydrogen atom on the monocyclic aryl group is R a Instead, multiple of the R 2 The structures are independent, such as: The n is selected from any positive integer from 1 to 3, and the plurality of R a Each is independently selected from hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted adamantyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylsilyl, substituted or unsubstituted alkylgermanyl.

[0014] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, the R... a The R group is selected from any one of substituted or unsubstituted alkoxy groups and substituted or unsubstituted isopropyl groups, wherein the substituted or unsubstituted alkoxy group is R a Structures such as -OR aa The R aa Each is independently selected from substituted or unsubstituted methyl, substituted or unsubstituted monocyclic aryl, or substituted or unsubstituted isopropyl.

[0015] The substituted or unsubstituted isopropyl R a Structure as The R ab Selected from substituted or unsubstituted methyl, unsubstituted ethyl, substituted or unsubstituted octyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted hexyl, substituted or unsubstituted nonyl, substituted or unsubstituted decyl, substituted or unsubstituted undecyl to hexadecyl, substituted or unsubstituted cyclohexane.

[0016] Or, the R a2 Selected from substituted ethyl groups, said R ab Any hydrogen atom is replaced by tert-butyl and ethyl groups.

[0017] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, the R... a Selected from alkylsilyl groups, wherein the alkylsilyl structure is as follows: The R acSelected from methyl, ethyl, tert-butyl, n-butyl, n-octyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, cyclohexyl, and the plurality of R ad Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-hexyl.

[0018] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, the R... ac Selected from ethyl, wherein any hydrogen atom on the ethyl group is substituted with a monocyclic aryl group, wherein R ac Selected from tert-butyl, wherein any hydrogen atom on the tert-butyl group is replaced by an isopropyl group.

[0019] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, the R... a Selected from alkylgermanium groups, wherein the alkylgermanium group has a structure such as: -Ge(R ae )3, multiple R ae Each is independently selected from methyl and ethyl.

[0020] In some cinchona alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of general formula I as described in the first aspect, or their tautomers, enantiomers, or diastereomers, the R... a Selected from methyl, wherein any hydrogen atom on the methyl group is replaced by a halogen.

[0021] The second aspect of this invention proposes a specific form of the cinchonasal alkaloid-derived tetrazolium tridentate N,N,P-ligand described in the first aspect, with the structure shown below:

[0022] A third aspect of this invention provides a method for preparing the cinchonasal alkaloid-derived tetrazolium tridentate N,N,P-ligand described in the first aspect, comprising the following steps:

[0023] Reaction 1:

[0024] Compound S2 reacts with diethyl phosphite to give intermediate S3;

[0025] Reaction 2:

[0026] Intermediate S3 reacts with methyl o-iodobenzoate to give intermediate S4;

[0027] Reaction 3:

[0028] Intermediate S4 and arylboronic acid (i.e., R) 2 The reaction of B(OH)2) yields intermediate S5;

[0029] Reaction 4:

[0030] Intermediate S5 is deoxygenated to obtain intermediate S6;

[0031] Reaction 5:

[0032] Hydrolysis of intermediate S6 yields intermediate S7;

[0033] Reaction 6:

[0034] Intermediate S7 and quinine derivative S8 undergo a condensation reaction to obtain the product;

[0035] The R 1 Selected from ethyl;

[0036] The R 2 As defined in any embodiment of the first aspect;

[0037] The R 3 Selected from methoxy groups.

[0038] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction 1 is carried out in the presence of a catalyst, a basic reagent and a solvent, and under an inert gas atmosphere or a nitrogen atmosphere.

[0039] In some embodiments of the preparation method described in the third aspect of the present invention, the catalyst for reaction 1 includes cuprous iodide.

[0040] In some embodiments of the preparation method described in the third aspect of the present invention, the alkaline reagent of reaction 1 includes potassium carbonate.

[0041] In some embodiments of the preparation method described in the third aspect of the present invention, the solvent of reaction 1 includes toluene.

[0042] In some embodiments of the preparation method described in the third aspect of the present invention, the inert gas in the inert gas atmosphere of reaction 1 includes at least one of helium, neon, argon, krypton, and xenon.

[0043] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction temperature of reaction 1 is the reflux temperature.

[0044] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction 2 is carried out in the presence of a catalyst, a basic reagent and a solvent, and under an inert gas atmosphere or a nitrogen atmosphere.

[0045] In some embodiments of the preparation method described in the third aspect of the present invention, the catalyst for reaction 2 comprises tetrakis(triphenylphosphine)palladium.

[0046] In some embodiments of the preparation method described in the third aspect of the present invention, the alkaline reagent of reaction 2 includes sodium carbonate.

[0047] In some embodiments of the preparation method described in the third aspect of the present invention, the solvent for reaction 2 includes at least one of toluene and water.

[0048] In some embodiments of the preparation method described in the third aspect of the present invention, the inert gas in the inert gas atmosphere of reaction 2 includes at least one of helium, neon, argon, krypton, and xenon.

[0049] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction temperature of reaction 2 is the reflux temperature.

[0050] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction 3 is carried out in the presence of a catalyst and a solvent.

[0051] In some embodiments of the preparation method described in the third aspect of the present invention, the catalyst for reaction 3 comprises triphenylphosphine.

[0052] In some embodiments of the preparation method described in the third aspect of the present invention, the solvent for reaction 3 includes at least one of toluene and tetrahydrofuran.

[0053] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction temperature of reaction 3 is the reflux temperature.

[0054] In some embodiments of the preparation method described in the third aspect of the present invention, reaction 4 is carried out in the presence of a base and a solvent.

[0055] In some embodiments of the preparation method described in the third aspect of the present invention, the base in reaction 4 includes lithium hydroxide.

[0056] In some embodiments of the preparation method described in the third aspect of the present invention, the solvent for reaction 4 includes at least one selected from water and tetrahydrofuran.

[0057] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction temperature of reaction 4 is the reflux temperature.

[0058] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction 5 is carried out in the presence of a condensing agent, a catalyst and a solvent.

[0059] In some embodiments of the preparation method described in the third aspect of the present invention, the condensing agent of reaction 5 includes either EDCI (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride) or DCC.

[0060] In some embodiments of the preparation method described in the third aspect of the present invention, the catalyst for reaction 5 includes DMAP (4-dimethylaminopyridine).

[0061] In some embodiments of the preparation method described in the third aspect of the present invention, the solvent of reaction 5 includes dichloromethane.

[0062] In some embodiments of the preparation method described in the third aspect of the present invention, the reaction temperature of reaction 5 is room temperature.

[0063] A fourth aspect of this invention provides an asymmetric catalytic method for α-methylbenzylamine, comprising:

[0064] Compound 1, Compound 2, and an organic solvent were added to a reaction system consisting of a copper salt, a ligand, and a base. The reaction was carried out under light irradiation at a wavelength of 350–400 nm to obtain product a1.

[0065] Magnesium metal and compound a1 were mixed, followed by the addition of alcohol. The reaction was carried out under controlled temperature, and then an organic solution of hydrochloric acid was added to alkalize the mixture, yielding product a2.

[0066] In some embodiments of the method described in the fourth aspect of the invention, the reaction to obtain product a1 is carried out under an inert gas atmosphere or a nitrogen atmosphere.

[0067] In some embodiments of the method described in the fourth aspect of the present invention, the reaction temperature for obtaining product a1 is room temperature.

[0068] In some embodiments of the method described in the fourth aspect of the present invention, the inert gas in the inert gas atmosphere includes at least one of helium, neon, argon, krypton, and xenon.

[0069] In some embodiments of the method described in the fourth aspect of the present invention, the wavelength includes 350 nm, 360 nm, 370 nm, 380 nm, 390 nm or 400 nm.

[0070] In some embodiments of the method described in the fourth aspect of the present invention, the ligand is selected from cinchonasal alkaloid-derived tetrazolium tridentate chiral N,N,P-ligand compounds of the general formula I described in the first aspect, or their tautomers, enantiomers, or diastereomers.

[0071] In some embodiments of the method described in the fourth aspect of the present invention, the copper salt comprises cuprous iodide.

[0072] In some embodiments of the method described in the fourth aspect of the present invention, the alkali includes cesium carbonate.

[0073] In some embodiments of the method described in the fourth aspect of the present invention, the organic solvent includes isopropyl ether.

[0074] In some embodiments of the method described in the fourth aspect of the present invention, the alcohol includes methanol.

[0075] In some embodiments of the method described in the fourth aspect of the present invention, the reaction temperature for obtaining product a2 is 0°C.

[0076] Terminology Explanation

[0077] The term "room temperature" refers to the ambient temperature, which can be 10℃ to 40℃, 15℃ to 35℃, or 20℃ to 30℃.

[0078] The terms "alkylsilyl" and "alkylsilyl" refer to the fact that the hydrogen atom in the silyl (-SiH3) group is independently replaced by one, two, or three alkyl groups. In some embodiments, the alkylsilyl group is a lower-order alkylsilyl group formed by one, two, or three C1-12 alkyl groups attached to a silicon atom. In other embodiments, the alkylsilyl group is a lower-order alkylsilyl group formed by one, two, or three C1-9 alkyl groups attached to a silicon atom. In still other embodiments, the alkylsilyl group is a lower-order alkylsilyl group formed by one, two, or three C1-6 alkyl groups attached to a silicon atom. In still other embodiments, the alkylsilyl group is a lower-order alkylsilyl group formed by one, two, or three C1-4 alkyl groups attached to a silicon atom. And in yet another embodiment, the alkylsilyl group is a lower-order alkylsilyl group formed by one, two, or three C1-3 alkyl groups attached to a silicon atom. Suitable alkylsilyl groups can be monoalkylsilyl, dialkylsilyl, or trialkylsilyl. Examples of alkylsilyl groups include, but are not limited to, trimethylsilyl (-Si(CH3)3), triethylsilyl (-Si(CH2CH3)3), tri-n-propylsilyl (-Si(CH2CH2CH3)3), etc.

[0079] The term "cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon group, the carbon ring of which may contain 3 to 20 carbon atoms, preferably 3 to 12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12) carbon atoms, and more preferably 3 to 6 carbon atoms. The partially unsaturated monocyclic or polycyclic cyclic hydrocarbon group is a saturated cycloalkyl group or may optionally contain one, two, or more double and / or triple bonds on its ring, thereby forming a so-called cycloalkenyl or cycloynyl group.

[0080] Unless otherwise stated, all chemicals were purchased commercially available and did not undergo further purification. Solvents such as dichloromethane and tetrahydrofuran used in the experiments were anhydrous. Thin-layer chromatography (TLC) was performed using 60F254 silica gel plates. Silica gel column chromatography was performed using Qingdao marine silica gel (particle size 0.040-0.063 mm). TLC development was performed using UV light (254 nm) or iodine. NMR spectra were characterized using a Bruker DPX 400 nuclear magnetic resonance instrument. 1 ¹H NMR was performed at 400 MHz using deuterated chloroform as the solvent and tetramethylsilane (TMS) as an internal standard. Chemical shifts are expressed in ppm, and coupling constants are expressed in Hz. 1 In H NMR, δ represents chemical shift, s represents singlet, d represents doublet, t represents triplet, q represents quartet, p represents quintet, and m represents multiplet.

[0081] The term "halogen" as used in this article refers to fluorine, chlorine, bromine, and iodine.

[0082] “Cy” indicates cyclohexyl.

[0083] “Me” stands for methyl.

[0084] “Et” represents ethyl.

[0085] The present invention has the following beneficial effects:

[0086] This invention utilizes cinchona bark tetrazolium derivatives and sterically hindered trivalent phosphorus as the core framework to develop a novel class of tridentate N,N,P-ligands (named Zhang Yufeng-type chiral anionic ligands), which have been successfully applied to asymmetric catalytic reactions. These novel chiral ligands possess rich structural features; the electronic and steric effects of the aryl substituents on the trivalent phosphorus are tunable, and additional weak interactions can be provided through the alkyl chain, thereby inducing excellent enantioselectivity. They exhibit advantages over existing ligands in terms of stereoselectivity and reaction efficiency. Therefore, the ligands provided by this invention can realize a wider range of asymmetric reactions. The ligands of this invention can be widely applied to stereoaggregate radical asymmetric cross-coupling reactions of secondary dialkyl-substituted haloalkanes and sulfinylimides, showing excellent application in the asymmetric cross-coupling of radicals to form α-chiral amines. They provide important guidance for developing novel catalytic systems to solve other types of stereoaggregate radical asymmetric reactions. Detailed Implementation

[0087] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0088] Step 1: Weigh magnesium shavings into a 500 mL double-necked flask containing a magnetic plunger. Place a reflux condenser over a constant-pressure dropping funnel on each flask and purge with argon gas for protection. Dissolve compound S1 (200 mmol) in 200 mL of tetrahydrofuran (THF) and add it to the flask via the constant-pressure dropping funnel. Slowly add the solution to the flask and incubate at 60 °C for 2 hours to prepare Grignard reagent S2. No further processing is required. Cool to 0 °C and add diethyl phosphite (60 mmol) dropwise. Slowly raise the temperature to room temperature and react for 2 hours. Post-processing: Add 200 mL of 3.0 M hydrochloric acid and stir until the solid is completely dissolved. Extract with ethyl acetate, separate the organic layer, dry with anhydrous sodium sulfate, filter, and concentrate under vacuum. The residue obtained is then subjected to silica gel column chromatography to give intermediate S3 (50% yield).

[0089] Step 2: Intermediate S3 (100 mmol), methyl o-iodobenzoate (150 mmol), alpha-methylbenzylamine (20 mmol), cuprous iodide (20 mmol), and potassium carbonate (300 mmol) were placed in a 500 mL round-bottom flask, purged three times with argon, and toluene (250 mL) was added. After reflux for 24 hours, the mixture was quenched with water, the organic layer was separated, extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain the product (40-80% yield).

[0090] Step 3: Intermediate S4 (100 mmol), arylboronic acid (RB(OH)2, 450 mmol), tetrakis(triphenylphosphine)palladium (5 mmol), and sodium carbonate (600 mmol) were placed in a 2000 mL round-bottom flask, purged three times with argon gas, and then toluene (600 mL) and water (600 mL) were added. After reflux for 24 hours, the mixture was extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue obtained was purified by silica gel column chromatography to give product S5 (40-80% yield).

[0091] Step 4: Intermediate S5 (100 mmol), triphenylphosphine (150 mmol), and trichlorosilane (1 mol) were placed in a 500 mL round-bottom flask, and toluene (100 mL) and tetrahydrofuran (100 mL) were added. The mixture was then refluxed for 24 hours, quenched with ice water, extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue was purified by silica gel column chromatography to give product S6 (60-80% yield).

[0092] Step 5: Intermediate S6 (100 mmol) and lithium hydroxide (2 mol) were placed in a 500 mL round-bottom flask, and water (150 mL) and tetrahydrofuran (150 mL) were added. After reflux for 24 hours, the solid was dissolved in 3.0 M hydrochloric acid, extracted three times with ethyl acetate, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue obtained was purified by silica gel column chromatography to give product S7 (60-80% yield).

[0093] Step 6: Intermediate S7 (100 mmol), intermediate S8 (100 mmol), EDCI (150 mmol), and DMAP (10 mmol) were placed in a 500 mL round-bottom flask, and dichloromethane (DCM) (250 mL) was added. After reacting at room temperature for 16 hours, the reaction was quenched with saturated ammonium chloride solution, and the mixture was extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue obtained was purified by silica gel column chromatography, and depending on the arylboronic acid added, the final product ligands 1 to 53 were obtained (50-80% yield).

[0094] Characterization data of ligand 1: 1 H NMR (400MHz, CDCl3) δ8.16(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.71(s,1H),7.70-7.65(m,5H),7.62-7.52(m,10H),7.48 (t,J=2.1Hz,2H),7.47-7.41(m,9H),7.40-7.35(m,5H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H) ,3.47(dt,J=6.6,5.5Hz,1H),2.98(ddd,J=12.1,7.1,4.6Hz,1H),2.89-2.81(m,1H),2.81-2.64(m,2H),2.05(dtt,J=6.6,5.3 ,3.8Hz,1H),1.92(dt,J=12.5,5.5Hz,1H),1.85-1.51(m,4H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0095] Characterization data of ligand 2: 1 HNMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,1H),8.07-7.89(m,8H),7.85-7.66(m,12H),7.66-7 .35(m,20H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt, J=6.6,5.5Hz,1H),3.39-2.62(m,5H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt,J=12.5,5 .5Hz,1H),1.82-1.49(m,4H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0096] Characterization data of ligand 3: 1HNMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,1H),8.06(t,J=1.9Hz,2H),8.02-7.88(m,16H),7.74-7.65(m, 6H),7.65-7.46(m,15H),7.44-7.37(m,2H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3 .83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.36-2.64(m,4H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt ,J=12.5,5.5Hz,1H),1.84-1.51(m,4H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0097] Characterization data of ligand 4: 1 HNMR(400MHz, CDCl3)δ8.56-8.48(m,2H),8.38(d,J=2.4Hz,2H),8.21-8.14(m,10 H),8.14-8.09(m,2H),8.03(t,J=2.1Hz,1H),8.00(d,J=8.7Hz,1H),7.79(td,J=1 3.3,2.2Hz,2H),7.75-7.68(m,6H),7.66-7.53(m,20H),7.49(dddd,J=11.2,7.1, 4.1,1.8Hz,1H),7.42(s,1H),7.39(td,J=7.5,1.4Hz,1H),7.23(dd,J=8.6,2.7Hz ,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.37 -2.67(m,5H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt,J=12.5,5.5Hz,1H),1. 84-1.73(m,2H),1.69(dddd,J=11.9,7.1,4.7,3.9Hz,1H),1.59(dddd,J=12.4,7. 3, 4.8, 4.0Hz, 1H), 1.42 (qdd, J=7.6, 6.1, 5.0Hz, 2H), 0.87 (td, J=7.5, 1.5Hz, 3H).

[0098] Characterization data of ligand 5: 1H NMR (400MHz, CDCl3) δ8.66 (dd, J = 8.4, 1.3Hz, 2H), 8.21-8.05 (m, 6H), 8.02-7.94 (m, 10H), 7.92-7.85 (m, 4H), 7.85-7.6 8(m,12H),7.66-7.45(m,12H),7.45-7.35(m,3H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H) ,3.47(dt,J=6.6,5.5Hz,1H),3.02-2.64(m,5H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt,J=12.5,5.5Hz,1H),1.84 -1.64(m,3H),1.59(dddd,J=12.4,7.3,4.8,4.0Hz,1H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0099] Characterization data of ligand 6: 1 HNMR (400MHz, CDCl3) δ8.25-8.05 (m, 2H), 8.00 (d, J = 8.7Hz, 1H), 7.75-7.53 (m,5H),7.53-7.44(m,9H),7.44-7.33(m,12H),7.23(dd,J=8.6,2.7Hz,1H), 5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.34 -2.64(m,5H),2.14-1.45(m,8H),1.34(s,36H),0.87(td,J=7.5,1.5Hz,3H).

[0100] Characterization data of ligand 7: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.89(t,J=2.2Hz,1H),7.77-7.31(m,16H),7.31-7.13(m,9 H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.55-2.64(m,6H),2.40(s,12H),2.15-1.32(m,8H),0.87(td,J=7.5,1.5Hz,3H).

[0101] Characterization data of ligand 8: 1 HNMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.75-7.63 (m,1H),7.60(ddd,J=13.3,7.1,1.4Hz,1H),7.53-7.33(m,10H),7.33-7.09(m, 12H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3. 34-2.64(m,5H),2.24(s,24H),2.10-1.29(m,8H),0.87(td,J=7.5,1.5Hz,3H).

[0102] Characterization data of ligand 9: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.80(t,J=2.1Hz,1H),7.77-7.52(m,11H),7.49( dddd,J=8.9,7.1,4.1,2.0Hz,1H),7.44-7.33(m,8H),7.33-7.14(m,5H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3. 61-3.41(m,3H),3.37-2.84(m,3H),2.81-2.62(m,2H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt,J=12.5,5.4Hz,1 H),1.84-1.49(m,4H),1.42(qdd,J=7.6,6.1,4.9Hz,4H),1.29(dd,J=25.0,6.7Hz,24H),0.87(td,J=7.5,1.5Hz,3H).

[0103] Characterization data of ligand 10: 1H NMR(400MHz, CDCl3)δ8.45(t,J=2.0Hz,2H),8.25-8.05(m,18H),8.05-7.92(m,2H),7.83-7.66(m,8 H),7.61(tdd,J=13.3,7.0,1.4Hz,1H),7.55-7.36(m,18H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J =8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.36-2.88(m,2H),2.88-2.64(m,3H),2 .12-1.82(m,2H),1.82-1.49(m,4H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0104] Characterization data of ligand 11: 1 HNMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,2H),7.80-7.35(m,11H),7.32(s,8H),7. 23(dd,J=8.6,2.7Hz,2H),6.86(ddd,J=2.7,1.6,0.7Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3 .47(dt,J=6.6,5.5Hz,1H),3.37-2.59(m,5H),2.17(s,24H),2.05(dtt,J=6.6,5.3,3.8Hz,1H),1.92(dt ,J=12.5,5.5Hz,1H),1.84-1.49(m,4H),1.42(qdd,J=7.6,6.1,5.0Hz,2H),0.87(td,J=7.5,1.5Hz,3H).

[0105] Characterization data of ligand 12: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.91(t,J=2.1Hz,1H),7 .77-7.66(m,8H),7.61(tdd,J=13.2,7.0,1.3Hz,2H),7.53-7.46(m,6H),7.46-7.31(m,6H) ,7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5. 5Hz,1H),3.37-2.59(m,5H),2.10-1.51(m,6H),1.35(s,74H),0.87(td,J=7.5,1.5Hz,3H).

[0106] Characterization data of ligand 13: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.83(t,J=2.2Hz ,1H),7.77-7.30(m,10H),7.23(dd,J=8.6,2.7Hz,1H),6.97(d,J=2.0Hz,8H),6.50( t,J=2.1Hz,4H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,24H),3.82(s,3H),3.47(dt,J =6.6,5.5Hz,1H),3.37-2.59(m,5H),2.12-1.32(m,8H),0.87(td,J=7.5,1.5Hz,3H).

[0107] Characterization data of ligand 14: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.82(d,J=2.2Hz,1H),7.77-7.53(m,8H) ,7.53-7.33(m,3H),7.23(dd,J=8.6,2.7Hz,1H),7.05(d,J=2.0Hz,8H),6.48(t,J=2.2Hz,4H),5.23(dd,J=8 .5,6.5Hz,1H),4.68(hept,J=5.7Hz,8H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.34-2.62(m,5H),2.07 -1.48(m,5H),1.42(qdd,J=7.6,6.1,4.9Hz,2H),1.32(dd,J=25.1,5.7Hz,48H),0.87(td,J=7.5,1.5Hz,3H).

[0108] Characterization data of ligand 15: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.82(t,J=2.2H z,1H),7.77-7.53(m,10H),7.53-7.27(m,16H),7.27-7.05(m,18H),7.05-6.91(m, 16H),6.43(t,J=2.2Hz,4H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J= 6.6,5.5Hz,1H),3.36-2.65(m,4H),2.10-1.20(m,8H),0.87(td,J=7.5,1.6Hz,3H).

[0109] Characterization data of ligand 16: 1 HNMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.09(t,J=2.2Hz,2H),8.05-7.92(m,10H),7.91(t,J=2.2Hz,1H),7.77-7.53(m,9H),7.53-7.31(m ,3H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.55-2.62(m,5H),2.12-1.27(m,8H),0.87(td,J=7.5,1.5Hz,3H).

[0110] Characterization data of ligand 17: 1 HNMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.80-7.53(m,8H),7.53-7.35(m,10H),7.23(dd,J=8.6,2.7Hz,2H), 5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.80(s,12H),3.53-2.56(m,6H),2.17(s,24H),2.09-1.29(m,8H),0.87(td,J=7.5,1.5Hz,3H).

[0111] Characterization data of ligand 18: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.83(t,J= 2.2Hz,1H),7.77-7.33(m,15H),7.23(dd,J=8.6,2.8Hz,1H),5.22(dd,J=8.6, 6.6Hz,1H),3.83(s,3H),3.77(s,12H),3.47(dt,J=6.6,5.5Hz,1H),3.34-2.5 9(m,5H),2.23-1.96(m,74H),1.96-1.26(m,57H),0.87(td,J=7.5,1.5Hz,3H).

[0112] Characterization data of ligand 19: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,1H),8.00(d,J=8.7Hz,1H),7.83(t,J=2. 2Hz,2H),7.77-7.53(m,8H),7.53-7.33(m,10H),7.23(dd,J=8.6,2.7Hz,2H),5.2 2(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.77(s,12H),3.47(dt,J=6.6,5.5Hz,1H), 3.37-2.61(m,4H),2.10-1.48(m,5H),1.42(s,74H),0.87(td,J=7.5,1.5Hz,3H).

[0113] Characterization data of ligand 20: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz ,2H),7.80-7.66(m,7H),7.66-7.30(m,12H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J =8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.58(m,5H),2.10 -1.49(m,22H),1.49-1.23(m,50H),0.87(td,J=7.5,1.5Hz,3H),0.79-0.60(m,24H).

[0114] Characterization data of ligand 21: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1H z,2H),7.80-7.66(m,7H),7.66-7.36(m,9H),7.33(d,J=2.1Hz,4H),7.23(dd,J=8. 6,2.7Hz,1H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H ),3.39-2.61(m,4H),2.07-1.45(m,20H),1.45-1.16(m,68H),0.94-0.66(m,27H).

[0115] Characterization data of ligand 22: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz,2H),7.8 0-7.66(m,8H),7.66-7.30(m,12H),7.23(dd,J=8.6,2.7Hz,1H),5.52(dt,J=10.3,5.8Hz,1H) ,3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.23(tq,J=5.8,1.0Hz,2H),2.98(ddd,J=12.1,7. 1,4.6Hz,1H),2.91-2.61(m,3H),2.12-1.49(m,15H),1.49-1.16(m,62H),1.07-0.71(m,52H).

[0116] Characterization data of ligand 23: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz,2H),7.80-7.66( m,6H),7.66-7.30(m,14H),7.23(dd,J=8.6,2.7Hz,1H),5.52(dt,J=10.3,5.8Hz,1H),5.36(ddt,J=10. 4,2.0,1.1Hz,1H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.23(ddt,J =6.9,5.8,1.1Hz,2H),3.06-2.62(m,4H),2.12-1.49(m,18H),1.49-1.15(m,90H),1.10-0.75(m,51H).

[0117] Characterization data of ligand 24: 1 HNMR(400MHz, CDCl3)δ8.16(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.77-7.6 3(m,7H),7.63-7.17(m,12H),7.11(d,J=2.2Hz,4H),5.23(dd,J=8.5,6.5Hz,1 H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.23(tq,J=5.8,1.0Hz,2H),3.0 3-2.59(m,4H),2.15-1.51(m,28H),1.51-1.15(m,114H),1.04-0.79(m,51H).

[0118] Characterization data of ligand 25: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz,1H ),7.78-7.64(m,6H),7.64-7.52(m,1H),7.52-7.36(m,6H),7.33(d,J=2.1Hz,8H),7.23 (dd,J=8.6,2.7Hz,1H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5H z,1H),3.37-2.53(m,5H),2.04-1.49(m,18H),1.46-1.18(m,141H),0.98-0.63(m,51H).

[0119] Characterization data of ligand 26: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,3H),7.80-7.64(m,5H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,5H),2.14-1.48(m,40H),1.48-1.15(m,157H),0.98-0.63(m,30H).

[0120] Characterization data of ligand 27: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz,2H),7.75-7.66(m,7H),7.66-7.14(m,14 H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.59-2.54(m,6H),2.15-1.49(m,45H),1.49-1.10(m,168H),0.98-0.68(m,29H).

[0121] Characterization data of ligand 28: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,3H),7.80-7.64(m,6H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,5H),2.14-1.48(m,26H),1.48-1.15(m,202H),0.98-0.63(m,30H).

[0122] Characterization data of ligand 29: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,4H),7.80-7.64(m,5H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,4H),2.14-1.48(m,27H),1.48-1.15(m,218H),0.98-0.63(m,30H).

[0123] Characterization data of ligand 30: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,4H),7.80-7.64(m,5H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,4H),2.14-1.48(m,27H),1.48-1.15(m,234H),0.98-0.63(m,30H).

[0124] Characterization data of ligand 31: 1H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,4H),7.80-7.64(m,5H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,4H),2.14-1.48(m,27H),1.48-1.15(m,250H),0.98-0.63(m,30H).

[0125] Characterization data of ligand 32: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.05-7.85(m,4H),7.80-7.64(m,5H),7.64-7.16(m,16H),5.22(dd,J=8.6,6.6Hz, 1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.69(m,4H),2.14-1.48(m,27H),1.48-1.15(m,266H),0.98-0.63(m,30H).

[0126] Characterization data of ligand 33: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J =2.1Hz,2H),7.78-7.52(m,8H),7.52-7.30(m,5H),7.30-7.09(m,8H),5.22(d d,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.37-2.54(m, 4H), 2.12-1.35 (m, 96H), 1.33 (d, J=1.5Hz, 48H), 0.87 (td, J=7.5, 1.6Hz, 3H).

[0127] Characterization data of ligand 34: 1H NMR(400MHz, CDCl3)δ8.18(d,J=8.6Hz,2H),8.07-7.83(m,5H),7.80-7.53(m,5 H),7.53-7.35(m,5H),7.32(s,8H),7.23(dd,J=8.6,2.7Hz,2H),5.22(dd,J=8. 6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.51(m,4H),2.1 0-1.49(m,22H),1.49-1.18(m,50H),0.87(td,J=7.5,1.5Hz,3H),0.74(s,72H).

[0128] Characterization data of ligand 35: 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91(t,J=2.1Hz,2H),7.77-7. 66(m,5H),7.66-7.53(m,1H),7.49(ddt,J=9.4,5.3,2.1Hz,1H),7.46-7.36(m,2H),7.31(dd,J=9.6 ,2.2Hz,10H),7.23(dd,J=8.6,2.7Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6 .6,5.5Hz,1H),3.37-2.59(m,4H),2.10-1.49(m,26H),1.49-1.15(m,82H),0.88(t,J=6.4Hz,51H).

[0129] Characterization data of ligand 36: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.86-7.31(m,18H),7.23(dd,J=8.6,2.7Hz,2H),5.23( dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2. 62(m,5H),2.14-1.32(m,8H),0.87(td,J=7.5,1.5Hz,3H),0.32(s,72H).

[0130] Characterization data of ligand 37: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.88-7.31(m,18H),7.23(dd,J=8.6,2.7Hz,2H),5.22(dd,J=8 .6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.37-2.59(m,5H), 2.14-1.31(m,8H),0.92(s,72H),0.87(td,J=7.5,1.5Hz,3H),0.40(s,48H).

[0131] Characterization data of ligand 38: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91-7.66(m,15H ),7.61(tdd,J=13.2,7.0,1.4Hz,1H),7.55-7.33(m,3H),7.23(dd,J=8.6,2.7Hz,1H),5.22(dd,J=8.6,6.6Hz ,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.37-2.61(m,5H),2.12-1.51(m,6H),1.51-1.35(m,10H),1 .27(h,J=7.1Hz,8H),1.15-1.02(m,32H),0.94(t,J=7.2Hz,24H),0.87(td,J=7.5,1.5Hz,3H),0.28(s,48H).

[0132] Characterization data of ligand 39: 1H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.91-7.6 6(m,10H),7.61(tdd,J=13.2,7.0,1.3Hz,2H),7.53-7.35(m,6H),7.23(dd,J=8.6,2.7Hz,2H),5.23 (dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.37-2.64(m,5H),2.07-1.53(m, 6H),1.53-1.34(m,10H),1.34-1.16(m,65H),1.16-1.04(m,26H),0.94-0.80(m,40H),0.28(s,48H).

[0133] Characterization data of ligand 40: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.05-7.31(m,20H),7.23(dd,J=8.6,2.7Hz,2H),5.22 (dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.53(m,5H),2.12-0.75(m,211H),0.28(s,48H).

[0134] Characterization data of ligand 41: 1 HNMR(400MHz, CDCl3)δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.05-7.31(m,21H),7.23(dd,J=8.6,2.7Hz,2H),5.2 2(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.47(dt,J=6.6,5.5Hz,1H),3.39-2.53(m,5H),2.12-0.75(m,306H),0.28(s,48H).

[0135] Characterization data of ligand 42: 1H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.85-7.31(m,18H),7.23(dd,J=8.6,2 .8Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.55-2.62(m,6H),2.12-1.26(m,12H),1.02-0.71(m,103H),0.38(s,48H).

[0136] Characterization data of ligand 43: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.86-7.33(m,19H),7.23(dd,J=8.6,2.7Hz,2H ),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.56-2.62(m,6H),2.14-1.21(m,95H),0.87(td,J=7.5,1.6Hz,3H),0.41(d,J=1.5Hz,48H).

[0137] Characterization data of ligand 44: 1 HNMR (400MHz, CDCl3) δ8.32(dt,J=10.8,2.2Hz,4H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.89(d,J=2.2Hz,8H),7.85-7.30(m, 8H),7.23(dd,J=8.6,2.7Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.56-2.61(m,6H),2.10-1.31(m,8H),1.15-0.75(m,123H).

[0138] Characterization data of ligand 45: 1H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.86-7.31(m,16H),7.28-7.13(m,5H),5.22( dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.58-2.59(m,6H),2.20-1.31(m,24H),1.06(dd,J=25.0,7.0Hz,151H),0.87(td,J=7.5,1.5Hz,3H).

[0139] Characterization data of ligand 46: 1 HNMR(400MHz, CDCl3)δ8.33(dt,J=20.7,2.2Hz,4H),8.18(d,J=8.6Hz,2H),8.08-7.91(m,7H),7.86-7.31(m,12H),7.23(dd,J=8.6,2.7Hz, 2H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.63-2.47(m,6H),2.10-1.27(m,31H),1.27-1.05(m,48H),0.83(dd,J=25.0,8.2Hz,147H).

[0140] Characterization data of ligand 47: 1 HNMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.05-7.92(m,8H),7.81-7.31(m,13H),7.23(dd,J=8.6,2.7H z,2H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.55-2.61(m,6H),2.12-1.53(m,6H),1.53-1.15(m,97H),1.09-0.60(m,123H).

[0141] Characterization data of ligand 48: 1HNMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.07-7.91(m,8H),7.86-7.33(m,13H),7.23(dd,J =8.6,2.7Hz,2H),5.23(dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.55-2.59(m,6H),2.09-1.49(m,6H),1.49-0.66(m,316H).

[0142] Characterization data of ligand 49: 1 HNMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.03-7.88(m,7H),7.88-7.33(m,14H),7.23(dd,J =8.6,2.7Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.66-2.58(m,6H),2.15-1.49(m,6H),1.49-0.77(m,140H).

[0143] Characterization data of ligand 50: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.83-7.31(m,19H), 7.23(dd,J=8.6,2.7Hz,2H),5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.50-2.67(m,6H),2.06-0.79(m,258H).

[0144] Characterization data of ligand 51: 1 H NMR (400MHz, CDCl3) δ8.31(t,J=2.2Hz,2H),8.18(d,J=8.6Hz,2H),8.00(d,J=8.7Hz,2H),7.85-7.30(m,19H),7.30-7.08(m,34H),5.22(dd,J=8.6 ,6.6Hz,1H),3.83(s,3H),3.56-2.61(m,6H),2.56-2.36(m,16H),2.10-1 .34(m,47H),1.05(dd,J=25.0,7.4Hz,96H),0.87(td,J=7.5,1.5Hz,3H).

[0145] Characterization data of ligand 52: 1 H NMR (400MHz, CDCl3) δ8.25-8.07(m,5H),8.00(d,J=8.7Hz,2H),7.80-7.33(m,18H),7.23(dd,J=8.6,2.7Hz,2H),5.23 (dd,J=8.5,6.5Hz,1H),3.83(s,3H),3.56-2.65(m,6H),2.15-1.32(m,7H),0.87(td,J=7.5,1.5Hz,3H),0.61(s,72H).

[0146] Characterization data of ligand 53: 1 H NMR (400MHz, CDCl3) δ8.27-8.07(m,5H),8.00(d,J=8.7Hz,2H),7.78-7.30(m,14H),7.23(dd,J=8.6,2.7Hz,2H),7.04(t,J=2.2Hz,4H) ,5.22(dd,J=8.6,6.6Hz,1H),3.83(s,3H),3.56-2.62(m,6H),2.14-1.31(m,55H),1.07(t,J=7.3Hz,72H),0.87(td,J=7.5,1.6Hz,3H).

[0147] The ligands of the present invention are applied to the stereopolymeric radical asymmetric cross-coupling reaction of secondary unactivated dialkyl halogenated alkanes and sulfinyl imides.

[0148] CuI (cuprous iodide, 0.1 equivalent), ligand 37 (0.15 equivalent), and Cs₂CO₃ (cesium carbonate, 4.0 equivalent) were added to a Schlenk tube equipped with a magnetic stir bar and dried in an oven. Argon gas was purged three times. Then, compound 1 (secondary iodoalkane, 0.2 mmol, 1 equivalent), compound 2 (di-4-methylphenylsulfinylimide, 0.2 mmol, 1 equivalent), and isopropyl ether ( i Pr₂O (4.0 mL) was then reacted at room temperature for 72 h under 390 nm LED light (10 W) illumination. After the reaction was complete (monitored by TLC), the precipitate was filtered off and washed with ethyl acetate. The solution was then evaporated and purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1) to give product a1 in 62% yield and 79% ee.

[0149] Characterization data of product a1: It is an oily liquid. HPLC conditions: Chiralcel IA (n-hexane / isopropanol = 90 / 10, flow rate 1.0 mL / min, λ = 254 nm), t R (minor) = 6.56min,t R (major) = 12.83 min. 1 H NMR (400MHz, CDCl3) δ7.88(d,J=8.4Hz,2H),7.79(d,J=8.3Hz,2H),7.23(d,J=8.1Hz,4H),2.98-2.89(m,1H), 2.36(s,6H),2.03-1.96(m,1H),1.80-1.73(m,3H),1.69-1.61(m,1H),1.41-1.32(m,1H),1.30-0.92(m,8H). 13 C NMR (100MHz, CDCl3) δ142.6,142.5,139.4,138.4,129.6,129.5,128.8,128.5,55.4,46.1,29.8,29.6,26.8,26.6,21.8,21.4. . HRMS(ESI) m / z Precise Mass Calculation C 20 H 30 NOS[M+H] + 356.2043, measured value 356.2031.

[0150] Product a1 was protected by desulfinylation to give compound a2:

[0151] Magnesium shavings (10 equivalents) and compound a1 (1 equivalent) were added to a Schlenk tube equipped with a magnetic stir bar and dried in an oven. Argon gas was purged three times, followed by the addition of methanol (MeOH, 0.1 M). The mixture was then stirred at 0°C until the magnesium shavings were completely dissolved, and the reaction was allowed to proceed to room temperature for 1 hour. After the reaction was complete (monitored by TLC), the system was cooled to 0°C, and a 1,4-dioxane solution of 4.0 mol / L hydrochloric acid was added. After the reaction was complete (monitored by TLC), the mixture was dissolved in water and washed with ethyl acetate. The aqueous phase was alkalized with ammonia, extracted three times with ethyl acetate, and concentrated to give product a2 in 90% yield.

[0152] The reaction results of existing ligands La to Li with the ligands of the present invention are shown in the table below (L1 represents ligand 1, and so on):

[0153] The reaction results for preparing product a1 are shown in the table below (L1 represents ligand 1, and so on):

[0154] It is evident that, in the stereopolymeric radical asymmetric cross-coupling reaction of secondary unactivated haloalkanes and sulfinylimides, the ligands of this invention exhibit advantages over existing ligands in both stereoselectivity and reaction efficiency. Therefore, designing novel multidentate anionic ligands can realize a wider range of asymmetric reactions.

[0155] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A compound, characterized in that, Selected from: tetrazolium tridentate chiral N,N,P-ligand compounds derived from cinchona alkaloids as shown in Formula I, or their tautomers, enantiomers, and diastereomers: Wherein, the R 1 Selected from substituted or unsubstituted alkyl groups; The R 2 Each is independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted monocyclic aryl, or C6-C14 substituted or unsubstituted fused ring groups; The R 3 Selected from alkoxy groups; The carbon atom marked with * is an R configuration, an S configuration, or an achiral carbon atom.

2. The compound according to claim 1, characterized in that, Multiple R 2 Each of the fused ring groups is independently selected from C6 to C14, wherein the fused ring group is formed by the fusion of at least one first ring and at least one second ring, wherein the first ring is selected from C3 to C6 cycloalkyl and the second ring is selected from monocyclic aryl; or Multiple R 2 Each is independently selected from substituted or unsubstituted naphthalene rings, substituted or unsubstituted anthracene rings, and substituted or unsubstituted phenanthrene rings.

3. The compound according to claim 1, characterized in that, Multiple R 2 Each is independently selected from a monocyclic aryl group, wherein any hydrogen atom on the monocyclic aryl group is R a Instead, multiple of the R 2 The structures are independent, such as: The n is selected from any positive integer from 1 to 3, and the plurality of R a Each is independently selected from hydrogen, unsubstituted methyl, substituted or unsubstituted adamantyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted butyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylsilyl, substituted or unsubstituted alkylgermanyl. Or, the R a Selected from methyl, wherein any hydrogen atom on the methyl group is replaced by a halogen.

4. The compound according to claim 3, characterized in that, The R a The R group is selected from any one of substituted or unsubstituted alkoxy groups and substituted or unsubstituted isopropyl groups, wherein the substituted or unsubstituted alkoxy group is R a Structures such as -OR aa The R aa Each is independently selected from substituted or unsubstituted methyl, substituted or unsubstituted monocyclic aryl, or substituted or unsubstituted isopropyl. The substituted or unsubstituted isopropyl R a Structure as The R ab Selected from substituted or unsubstituted methyl, unsubstituted ethyl, substituted or unsubstituted octyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted hexyl, substituted or unsubstituted nonyl, substituted or unsubstituted decyl, substituted or unsubstituted undecyl to hexadecyl, substituted or unsubstituted cyclohexane. Or, the R ab Selected from substituted ethyl groups, the R ab Any hydrogen atom is replaced by tert-butyl and ethyl groups.

5. The compound according to claim 3, characterized in that, The R a Selected from alkylsilyl groups, wherein the alkylsilyl structure is as follows: The R ac Selected from methyl, ethyl, tert-butyl, n-butyl, n-octyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclohexyl, and multiple Rs. ad Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-hexyl.

6. The compound according to claim 5, characterized in that, The R ac Selected from ethyl, wherein any hydrogen atom on the ethyl group is substituted with a monocyclic aryl group, wherein R ac Selected from tert-butyl, wherein any hydrogen atom on the tert-butyl group is replaced by an isopropyl group.

7. The compound according to claim 3, characterized in that, The R a Selected from alkylgermanium groups, wherein the alkylgermanium group has a structure such as: -Ge(R ae )3, multiple R ae Each is independently selected from methyl and ethyl.

8. The compound according to claim 1, wherein the compound is selected from the following structures:

9. A method for preparing a cinchona alkaloid-derived tetrazolium tridentate N,N,P-ligand, comprising the following steps: Reaction 1: Compound S2 reacts with diethyl phosphite to give intermediate S3; Reaction 2: Intermediate S3 reacts with methyl o-iodobenzoate to give intermediate S4; Reaction 3: Intermediate S4 reacts with arylboronic acid to give intermediate S5; Reaction 4: Intermediate S5 is deoxygenated to obtain intermediate S6; Reaction 4: Hydrolysis of intermediate S6 yields intermediate S7; Reaction 5: Intermediate S7 and quinine derivative S8 undergo a condensation reaction to obtain the product; The R 1 Selected from ethyl; The R 2 As defined in any one of claims 1 to 8; The R 3 Selected from methoxy groups.

10. An asymmetric catalytic method for α-methylbenzylamine, comprising: Compound 1, Compound 2, and an organic solvent were added to a reaction system consisting of a copper salt, a ligand, and a base. The reaction was carried out under light irradiation at a wavelength of 350–400 nm to obtain product a1. Magnesium metal and compound a1 were mixed, followed by the addition of alcohol. The reaction was carried out under controlled temperature, and then an organic solution of hydrochloric acid was added to alkalize the mixture, yielding product a2.

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