Axially chiral nitrogen heterocyclic aromatic compounds, methods of synthesis and use thereof

Abstract

The application discloses a high-efficiency synthesis method of an axially chiral nitrogen hetero polyaromatic ring compound, which uses a pyridine alkyne-benzyne bisaromatic alkyne precursor as raw material, uses an alkali and a solvent to realize warm and mild hydrogenation of the bisaromatic alkyne precursor at a certain temperature, continuously obtains a pyridine alkyne-benzyne active intermediate, then a [4+2] cycloaddition reaction occurs, and a nitrogen hetero polyaromatic ring compound library is quickly and efficiently constructed, and the preparation method has wide application prospects.

Description

Technical Field

[0001] This invention belongs to the field of organic compound process application technology, and relates to an axially chiral nitrogen-containing heterocyclic aromatic compound, its synthesis method, and its application. Background Technology

[0002] In recent years, significant progress has been made in the application of organic materials. Polycyclic aromatic hydrocarbons (PAHs), as multifunctional compounds, have been widely used in electrodes, optoelectronic devices, and fluorescence-based materials. Introducing nitrogen into PAHs can bring new functionalities and enhance material stability, sparking a new wave of interest among organic and materials scientists, who have made many innovative contributions. Although bottom-up methods have enabled the high-temperature CC coupling synthesis of graphene nanoribbons, the coupling of nitrogen-doped PAHs remains relatively scarce. In 2015, Wang Zhaohui's team synthesized biperyleneimide through chlorination, hydrogenation, and bromination of peryleneimide, which can be used in solar cells with a photoelectric efficiency as high as 7.16% (at the time). In 2017, Klaus Müllen's team reported N-doped hexabenzo[a]carbamate, which, by introducing nitrogen atoms into the conjugated lattice to break the conjugated structure and introduce pyrazine rings, is a two-dimensional organic graphite material with anti-aromatic properties. Subsequently, Feng Xinliang's team developed an Rh-catalyzed cyclization method to synthesize cationic N-doped dibenzonaphthalene with a low HOMO / LUMO orbital band gap. Its radical-forming and cationic radical-forming properties can be used in optoelectronic materials. In 2021, Akimitsu Narita's team designed N-doped dibenzonaphthalene with high photostability and pH responsiveness. Its fluorescence characteristics can be altered through interactions with acids and metal cations, making it suitable for optical imaging. While chemists are actively exploring methods to synthesize these π-system N-PAHs, these molecules are relatively easy to obtain due to their symmetry. However, for constructing larger N-PAHs with π systems, stringent synthetic conditions remain a challenge, limiting their practical applications. Therefore, there is an urgent need to develop an efficient synthetic method. Summary of the Invention

[0003] To address the shortcomings of existing synthetic methods, the present invention aims to provide an efficient synthetic method for axially chiral nitrogen-containing heterocyclic aromatic hydrocarbons.

[0004] This invention enables hydrogen extraction from diaryryne precursors under very mild conditions through solvent and alkali selection, continuously yielding pyridyne-benzyne, and rapidly and efficiently constructing a library of nitrogen-containing heterocyclic aromatic compounds, compatible with alkyl, substituted aryl, and halogen compounds.

[0005] This invention provides a method for synthesizing axially chiral nitrogen-containing polyaromatic compounds, the specific steps of which are as follows:

[0006] Step (1): Using diarylcyclic pyridine high-iodide salt as raw material, pyridineyne or benzyne intermediate 1 is obtained under the action of alkali and solvent;

[0007] Step (2): Under the action of alkali and solvent, the pyridyne or benzyne intermediate 1 undergoes a rapid [4+2] cycloaddition reaction with the polyaromatic ring substituted diene to obtain the product;

[0008] Step (3): In a solvent, the product obtained in step (2) can be further hydrogenated under the action of an alkali to generate a second pyridyne or benzene intermediate 2;

[0009] Step (4): The pyridyne or benzyne intermediate 2 obtained in step (3) is further reacted with a polycyclic substituted diene in a [4+2] cycloaddition reaction to rapidly obtain an aza-polycyclic compound; the reaction equation is shown in equation A below:

[0010]

[0011] Among them, R 1 R 2 R 3 R 4 R 5 Each of the following is independently selected from one or more of hydrogen, alkyl, trifluoromethyl, trifluoromethoxy, aryl, silyl, and halogen;

[0012] R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 Each is independently one or more of hydrogen, alkyl, and aryl groups;

[0013] In the structural formula of the diaryl cyclic pyridine periodic salt, a and b represent selectivity only and can be omitted. Therefore, the structural formula of the diaryl cyclic pyridine periodic salt can be:

[0014] In step (1), the alkali is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA, preferably KOH or tBuOK.

[0015] In step (1), the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether. Preferably, toluene or acetonitrile is used as the solvent.

[0016] In step (1), based on diarylcyclic pyridine periodic salt, the volume of the solvent used is 0.5-10 mL; preferably, it is 1 mL.

[0017] In step (1), the molar ratio of the diarylcyclic pyridine periodic salt to the alkali is 1:1-5; preferably, it is 1:3.

[0018] In step (1), the reaction temperature is 0-80℃; preferably, it is room temperature.

[0019] In step (1), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0020] In step (2), the alkali is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA, preferably KOH or tBuOK.

[0021] In step (2), the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether. Preferably, toluene or acetonitrile is used as the solvent.

[0022] In step (2), based on diarylcyclic pyridine periodic salt, the volume of the solvent used is 0.5-10 mL; preferably, it is 1 mL.

[0023] In step (2), the molar ratio of the pyridyne or benzyne intermediate 1, the polyaromatic substituted diene, and the base is 1:1-5:1-5; preferably, it is 1:5:3.

[0024] In step (2), the reaction temperature is 0-80℃; preferably, it is room temperature.

[0025] In step (2), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0026] In step (3), the alkali is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA, preferably LiHMDS.

[0027] In step (3), the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether. Preferably, toluene or acetonitrile is used as the solvent.

[0028] In step (3), based on diarylcyclic pyridine periodic salt, the volume of the solvent used is 0.5-10 mL; preferably, it is 1 mL.

[0029] In step (3), the molar ratio of the product to the alkali is 1:1-5; preferably, it is 1:3.

[0030] In step (3), the reaction temperature is 0-80℃; preferably, it is room temperature.

[0031] In step (3), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0032] In step (4), the molar ratio of the pyridyne or benzyne intermediate 2 to the polyaromatic ring substituted diene is 1:1-5; preferably, it is 1:5.

[0033] In step (4), the reaction temperature is 0-80℃; preferably, it is room temperature.

[0034] In step (4), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0035] In step (2), the structural formula of the product includes the following:

[0036]

[0037] The polycyclic aromatic compounds obtained in step (4) have the following structural formulas:

[0038]

[0039]

[0040] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is one or more of hydrogen, alkyl, and aryl groups.

[0041] In this invention, the preparation method of the diarylcyclic pyridine periodic salt includes the following steps:

[0042] Step (1): Using substituted 2-halo-3-aminopyridine as a raw material, under the conditions of Pd catalyst, solvent, base and ligand, it undergoes Suzuki coupling reaction with polysubstituted arylboronic acid to obtain intermediate 1;

[0043] Step (2): The intermediate 1 obtained in step (1) is subjected to diazotization in the presence of acid, additives and solvent to replace the amino group with iodine to obtain intermediate 2;

[0044] Step (3): The intermediate 2 obtained in step (2) is oxidized in the presence of acid, oxidant, and solvent to obtain diarylpyridine periodic salt; the reaction equation is shown below:

[0045]

[0046] In the formula, R includes R 4 R 5 R' contains R 1 R 2 R 3 X is a halogen;

[0047] Among them, R 1 R 2 R 3 R 4 R 5 Each of the following is independently selected from one or more of hydrogen, alkyl, alkoxy, trifluoromethyl, trifluoromethoxy, aryl, silyl, and halogen.

[0048] Preferably,

[0049] R 1 It includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenoxthiazide, thianthracene, alkoxy, dimethylamino, and halogens.

[0050] R 2 It includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenoxthiazide, thianthracene, alkoxy, dimethylamino, and halogens.

[0051] R 3 It includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenoxthiazide, thianthracene, alkoxy, dimethylamino, and halogens.

[0052] R 4It includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenoxthiazide, thianthracene, alkoxy, dimethylamino, and halogens.

[0053] R 5 It includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenoxthiazide, thianthracene, alkoxy, dimethylamino, and halogens.

[0054] In step (1), the Pd catalyst is one or more of Pd(OAc)2, Pd(dba)2, Pd2(dba)3, Pd(Ph3P)4, PdCl2, Pd(MeCN)2Cl2, etc.; preferably, it is Pd(dba)2.

[0055] In step (1), the ligand is one or more of Dave-Phos, X-Phos, S-Phos, Ph3P, (Ph2P)2(CH2)2, (Ph2P)2(CH2)3, (Ph2P)2(CH2)4, tBu-Phos, etc.; preferably, it is X-Phos.

[0056] In step (1), the solvent is one or more of PhMe, MeOH, EtOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, DMF, etc.; preferably, it is a mixed solvent of PhMe, EtOH and H2O, with an optimal volume ratio of 5 / 1 / 5.

[0057] In step (1), the alkali is one or more of Na2CO3, K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, LDA, etc.; preferably, it is Na2CO3.

[0058] In step (1), the molar ratio of the substituted 2-halo-3-aminopyridine, the base, the Pd catalyst, and the ligand is 1:1-10:0.1-1:0.1-1; preferably, it is 1:5:0.02:0.04.

[0059] In step (1), the reaction temperature is room temperature - 120°C; preferably, it is 80-90°C.

[0060] In step (1), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0061] In step (2), the acid is one or more of H2SO4, HCl, TFA, TfOH, TsOH, HBF4, etc.; preferably, it is TfOH.

[0062] In step (2), the additive is one or more of NaNO2, KNO2, tBuONO, etc.; preferably, it is tBuONO.

[0063] In step (2), the solvent is one or more of PhMe, MeOH, EtOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, DMF, etc.; preferably, it is MeCN;

[0064] In step (2), the iodine source used is one or more of NaI, I2, KI, TBAI, etc.; preferably, it is TBAI.

[0065] In step (2), the molar ratio of intermediate 1, acid, additive, and iodine source is 1:1-10:0.5-2:0.5-2; preferably, it is 1:4:1.3:1.3.

[0066] In step (2), the reaction temperature is -80–100℃; preferably, it is -40℃.

[0067] In step (2), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0068] In step (3), the oxidant is one or more of H2O2, m-CPBA, NaIO4, etc.; preferably, it is m-CPBA.

[0069] In step (3), the acid is one or more of H2SO4, HCl, TFA, TfOH, TsOH, HBF4, etc.; preferably, it is TfOH.

[0070] In step (3), the solvent is one or more of PhMe, MeOH, EtOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, DMF, etc.; preferably, it is DCM.

[0071] In step (3), the molar ratio of intermediate 2, acid, and oxidant is 1:1-10:1-5; preferably, it is 1:4:1.75.

[0072] In step (3), the reaction temperature is -80–100℃; preferably, it is 0℃.

[0073] In step (3), the reaction time is 1-24 hours; preferably, it is 12 hours.

[0074] In one specific embodiment, the reaction steps are as follows: using substituted 2-halo-3-aminopyridine as a starting material, Pd(dba)2 as a catalyst, X-Phos as a ligand, and Na2CO3 as a base, Suzuki coupling is performed with a polysubstituted arylboronic acid at 90°C. Subsequently, diazotization is carried out at -40°C using tBuONO as an activating agent under the action of a strong acid TfOH, and nucleophilic substitution is performed using TBAI as an iodine source to obtain an iodine compound. Finally, under the action of TfOH at 0°C, oxidation is performed using mCPBA to obtain a diarylcyclic pyridine periodide. The reaction equation is shown below:

[0075]

[0076] The present invention also provides a diarylcyclic pyridine periodic salt obtained by the above method.

[0077] The diaryl cyclic pyridine high-iodine salt includes, but is not limited to, the following components:

[0078]

[0079] In this invention, the aza-polycyclic aromatic compound obtained from the two cycloaddition reactions is subjected to a one-step de-bibridged epoxide aromatization to yield an aza-polycyclic aromatic hydrocarbon compound, the structural formula of which is as follows:

[0080]

[0081] In Equation 1, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is one or more of hydrogen, alkyl, trifluoromethyl, substituted aryl, aryl, etc.;

[0082] Preferably,

[0083] Among them, R 1 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0084] Among them, R 2 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0085] Among them, R 3 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0086] Among them, R 4 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0087] Among them, R 5 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0088] Among them, R 6 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0089] Among them, R 7The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0090] Among them, R 8 The compounds are selected from hydrogen, alkyl, trifluoromethyl, aryl, and heterocyclic compounds, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, other alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-iodophenyl, 4-aldehydephenyl, 4-formylphenyl, other phenyl compounds, as well as pyrrole, indole, dibenzopyrrole, pyrazole, thiophene, thiazole, benzothiophene, benzothiazole, benzoisothiazole, dibenzothiophene, phenothiazine, thianthracene.

[0091] The nitrogen-containing polycyclic aromatic hydrocarbon compound, of formula (1), has a structure including but not limited to the following parts:

[0092]

[0093]

[0094]

[0095] The technical difficulty of this invention lies in:

[0096] 1) For the first time, pyridine periodide was used as a pyridyne precursor to generate pyridyne under mild conditions;

[0097] 2) For the first time, cyclic pyridine high-iodide salt was used as a precursor for diaromaticynes, which can generate aromaticynes twice in succession through [4+2] cycloaddition, thus efficiently and rapidly constructing N-PAHs;

[0098] 3) Cyclic pyridine periodocyanate has a single nucleophilic addition selectivity as an aromatic yne precursor, and the nucleophilic addition site is opposite to that of conventional aromatic yne precursors;

[0099] 4) This paper first proposed that the nucleophilic addition selectivity of aromatic yne directed groups is induced by aromatic yne directing groups, providing a feasible approach for the study of highly selective nucleophilic addition of aromatic yne;

[0100] 5) Iodine atoms have a large atomic radius and weak electron binding ability. They can not only serve as a good leaving group to generate aromatic yne, but also stabilize aromatic yne through hyperconjugation and regulate nucleophilic selective sites through push-pull effects.

[0101] 6) Pyridine periodide, as a precursor of this type of aromatic yne, has very gentle formation conditions, very simple synthesis conditions, and wide functional group compatibility, and has very broad potential application value.

[0102] The present invention also provides the application of the aforementioned nitrogen-containing polycyclic aromatic compounds in the synthesis of nitrogen-containing polycyclic aromatic hydrocarbons.

[0103] The present invention also provides the application of the aforementioned nitrogen-containing polycyclic aromatic hydrocarbon compounds in electrodes, optoelectronic devices, and fluorescence-based materials.

[0104] The beneficial effects of this invention include: the synthesis reaction conditions of the nitrogen-containing polycyclic aromatic hydrocarbons of this invention are mild, the operation is simple, and the selectivity is good, making it of great practical and research value. The nitrogen-containing polycyclic aromatic hydrocarbon compounds of this invention have the potential to become fluorescent materials, optoelectronic materials, and TADF materials. Detailed Implementation

[0105] The present invention will be further described in detail below with reference to specific embodiments. Except for the contents specifically mentioned below, the processes, conditions, and experimental methods for implementing the present invention are all common knowledge and general knowledge in the art, and the present invention does not have any particular limitations.

[0106] The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0107] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values.

[0108] Example 1

[0109] Synthesis of Compound 1

[0110] Using a 2-chloro-3-aminopyridine derivative (10 mmol) as a starting material, toluene, water, and ethanol (v / v / v = 5 / 1 / 5) as a mixed solvent, Pd(dba)₂ (2 mol%) as a catalyst, X-Phos (4 mol%) as a ligand, and Na₂CO₃ (5.0 equiv.) as a base, a substituted arylboronic acid compound (1.3 equiv.) was coupled at 90 °C to yield 2-aryl-3-aminopyridine compounds. Subsequently, at -40 °C, diazotization with tBuONO (1.3 equiv.) and iodination with TBAI (1.3 equiv.) were carried out in the presence of TfOH (4.0 equiv.) to yield 2-aryl-3-iodopyridine compounds. 2-aryl-3-iodopyridine compounds were oxidized by mCPBA (1.75 equiv.) in DCM solvent at 0 °C with TfOH (4.0 equiv.). The mixture was stirred at room temperature until a solid precipitated. After the reaction was complete, the solvent was evaporated to dryness. The mixture was washed with Et2O and filtered to obtain the product, diaryl cyclic pyridine periodide 1.

[0111] The characterization results of compound 1 are as follows:

[0112] 1 H NMR (500MHz, DMSO-d6) δ8.89(dd,J=4.6,1.0Hz,1H),8.52(d,J=8.3Hz,1H),8.24(d,J=8.7Hz,1H ),7.80(d,J=2.3Hz,1H),7.64(dd,J=8.3,4.6Hz,1H),7.43(dd,J=8.7,2.3Hz,1H),3.92(s,3H). 13 C NMR (125MHz, DMSO-d6) δ161.8,156.6,150.7,138.5,131.3,128.4,124.1,122.8,120.2(q ,J=320.0Hz),118.4,117.5,113.9,55.7.IR(neat)1285,1210,1117,1024,960,837,633cm -1 .HRMS(ESI)m / z:(M) + Calculated for C 12 H9INO + 309.9723; Found 309.9755.

[0113] Example 2

[0114] Synthesis of Compound 2

[0115] Using a 2-chloro-3-aminopyridine derivative (10 mmol) as a starting material, toluene, water, and ethanol (v / v / v = 5 / 1 / 5) as a mixed solvent, Pd(dba)₂ (2 mol%) as a catalyst, X-Phos (4 mol%) as a ligand, and Na₂CO₃ (5.0 equiv.) as a base, a substituted arylboronic acid compound (1.3 equiv.) was coupled at 90 °C to yield 2-aryl-3-aminopyridine compounds. Subsequently, at -40 °C, diazotization with tBuONO (1.3 equiv.) and iodination with TBAI (1.3 equiv.) were carried out in the presence of TfOH (4.0 equiv.) to yield 2-aryl-3-iodopyridine compounds. 2-aryl-3-iodopyridine compounds were oxidized by mCPBA (1.75 equiv.) at 0 °C with TfOH (4.0 equiv.) as solvent. The mixture was stirred at room temperature until a solid precipitated. After the reaction was complete, the solvent was evaporated to dryness. The mixture was washed with Et2O and filtered to obtain the product, diaryl cyclic pyridine periodic salt 2.

[0116] The characterization results of compound 2 are as follows:

[0117] 1 H NMR (500MHz, CD3OD) δ8.99(dd,J=4.6,1.1Hz,1H),8.58(d,J=8.6Hz,1H),8.53(dd,J=8.4,1 .1Hz,1H),8.17(d,J=1.0Hz,1H),7.86(dd,J=8.6,1.1Hz,1H),7.74(dd,J=8.4,4.6Hz,1H). 13 C NMR (125MHz, CD3OD) δ158.1,153.2,152.6,152.6,140.1,140.0,131.4,127.3,125.5,123.5,121.8(q,J= 257.5Hz),121.7(q,J=316.3Hz),121.6,120.3.IR(neat)1263,1224,1167,1024,997,799,631,625,574cm -1 .HRMS(ESI)m / z:(M) + Calculated for C 12 H6F3INO + 363.9441; Found 363.9433.

[0118] Example 3

[0119] Synthesis of Compound 3

[0120] Using a 2-chloro-3-aminopyridine derivative (10 mmol) as a starting material, toluene, water, and ethanol (v / v / v = 5 / 1 / 5) as a mixed solvent, Pd(dba)₂ (2 mol%) as a catalyst, X-Phos (4 mol%) as a ligand, and Na₂CO₃ (5.0 equiv.) as a base, a substituted arylboronic acid compound (1.3 equiv.) was coupled at 90 °C to yield 2-aryl-3-aminopyridine compounds. Subsequently, at -40 °C, diazotization with tBuONO (1.3 equiv.) and iodination with TBAI (1.3 equiv.) were carried out in the presence of TfOH (4.0 equiv.) to yield 2-aryl-3-iodopyridine compounds. 2-aryl-3-iodopyridine compounds were oxidized by mCPBA (1.75 equiv.) at 0 °C with TfOH (4.0 equiv.) as solvent. The mixture was stirred at room temperature until a solid precipitated. After the reaction was complete, the solvent was evaporated to dryness. The mixture was washed with Et2O and filtered to obtain the product, diaryl cyclic pyridine periodide 3.

[0121] The characterization results of compound 3 are as follows:

[0122] 1 H NMR (400MHz, DMSO-d6) δ8.97(d,J=4.6Hz,1H),8.56(d,J=8.3Hz,1H),8.41(dd,J=8.6,5.3Hz,1H),8.11–8.01(m,1H),7.72–7.83(m,2H). 13 C NMR (100MHz, DMSO-d6) δ163.5(d,J=252.0Hz),156.3,151.5,139.2,136.1,129.8(d,J=9.0Hz),125.8,122.5(d,J=10.0Hz),120 .7(q,J=320.0Hz),120.0,119.2(d,J=23.0Hz),117.5(d,J=27.0Hz).IR(neat)1280,1220,1128,1022,957,836,732,633,571cm -1 .HRMS(ESI)m / z:(M) + Calculated for C 11 H6FIN + 297.9523; Found 297.9515.

[0123] Example 4

[0124] Synthesis of Compound 4

[0125] Using a 2-chloro-3-aminopyridine derivative (10 mmol) as a starting material, toluene, water, and ethanol (v / v / v = 5 / 1 / 5) as a mixed solvent, Pd(dba)₂ (2 mol%) as a catalyst, X-Phos (4 mol%) as a ligand, and Na₂CO₃ (5.0 equiv.) as a base, a substituted arylboronic acid compound (1.3 equiv.) was coupled at 90 °C to yield 2-aryl-3-aminopyridine compounds. Subsequently, at -40 °C, diazotization with tBuONO (1.3 equiv.) and iodination with TBAI (1.3 equiv.) were carried out in the presence of TfOH (4.0 equiv.) to yield 2-aryl-3-iodopyridine compounds. 2-aryl-3-iodopyridine compounds were oxidized by mCPBA (1.75 equiv.) at 0 °C with TfOH (4.0 equiv.) as solvent. The mixture was stirred at room temperature until a solid precipitated. After the reaction was complete, the solvent was evaporated to dryness. The mixture was washed with Et2O and filtered to obtain the product, diaryl cyclic pyridine periodic salt 4.

[0126] The characterization results of compound 4 are as follows:

[0127] 1 H NMR (500MHz, DMSO-d6) δ8.48–8.54(m,2H),8.17–8.27(m,4H),7.88(t,J=7.4Hz,1H),7.80(dd,J=10.6,4.7Hz,1H),7.52–7.58(m,3H). 13 C NMR(125MHz,DMSO-d6)δ158.3,157.9,140.2,139.6,137.0,133.6,131.4,131.1,130.6,129.7,129.1 ,127.6,122.7,122.1,121.0(q,J=320.0Hz),117.7.IR(neat)1273,1223,1143,1025,740,632,612cm -1 .HRMS(ESI)m / z:(M) + Calculated for C 17 H 11 IN + 355.9931; Found 355.9944.

[0128] The following embodiments of the present invention relate to the preparation of polycyclic aromatic hydrocarbon compounds with reference to the following reaction formulas:

[0129]

[0130] Example 5

[0131] Synthesis of compound 5:

[0132]

[0133] The substrate (0.1 mmol), furan derivative (140 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to give a white solid 5 (43.9 mg, 69%).

[0134] The characterization results of compound 5 are as follows:

[0135] 1 H NMR (500MHz, (CD3)2CO) δ7.84–8.27(m,3H),7.27–7.79(m,9H),6.74–7.22(m,7H),6.59–6.71(m,1H),3.89(s,3H),3.73(s,3H). 13 C NMR (125MHz, (CD3)2CO) δ165.5,164.9,164.1,160.9,160.0,155.1,153.2,146.8,145.0,144.8,139.7,138.4,137.4,136 .2,130.7,129.8,129.2,128.0,127.8,124.0,121.3,119.4,114.7,112.7,112.1,98.6,93.7,93.2.HRMS(ESI)m / z:(M+H) + Calculated for C 35 H 27 INO3 + 636.1030; Found 636.1052.

[0136] Example 6

[0137] Synthesis of compound 6:

[0138]

[0139] The substrate (0.1 mmol), furan derivative (168 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to give a white solid 6 (35.3 mg, 51%).

[0140] The characterization results of compound 6 are as follows:

[0141] 1 H NMR(500MHz,(CD3)2CO)δ7.90–8.36(m,3H),7.49–7.73(m,5H),7.30–7.46(m,3H),6.85–7.12(m,1H),6.75–6.84( m,1H),6.61(d,J=8.5Hz,1H),3.88(s,3H),3.75(s,1H),2.42(s,3H),2.24(s,3H),2.00–2.14(m,3H),1.90(s,3H). 13 C NMR (125MHz, (CD3)2CO) δ158.5,158.3,145.9,145.9,144.7,139.7,136.7,129.7,129.7,129.5,129.5,129.2,129.2,127.9,12 7.8,126.9,126.7,126.5,126.3,112.5,112.5,108.5,108.4,107.7,107.6,100.7,55.7,18.6,11.9,11.7.HRMS(ESI)m / z:(M+H) + Calculated for C 39 H 35 INO3 + 692.1656; Found 692.1742.

[0142] Example 7

[0143] Synthesis of compound 7:

[0144]

[0145] The substrate (0.1 mmol), furan derivative (128 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green liquid 7 (40.4 mg, 73%).

[0146] The characterization results of compound 7 are as follows:

[0147] 1H NMR (400MHz, CDCl3) δ7.86–8.10(m,2H),7.53–7.85(m,4H),7.17–7.50(m,9H),6.95–7.10(m,1H),6.62–6.93(m,4H). 13 C NMR (100MHz, CDCl3) δ164.3,163.5,162.5,161.9,161.2,144.7,143.2,139.1,137.8,130.1,129.2,1 29.1,128.9,128.6,127.5,116.1,115.9,114.9,114.7,112.3,98.2,92.9,92.2.HRMS(ESI)m / z:(M+H) + Calculated for C 27 H 16 F3INO + 554.0223; Found 554.0266.

[0148] Example 8

[0149] Synthesis of compound 8:

[0150]

[0151] The substrate (0.1 mmol), furan derivative (160 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the solid was separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green solid 8 (47.3 mg, 70%).

[0152] The characterization results of compound 8 are as follows:

[0153] 1 H NMR (500MHz, CDCl3) δ8.40(s,1H),8.26–7.49(m,14H),7.46–7.19(m,7H),7.04–6.07(m,4H). 13C NMR (125MHz, CDCl3) δ162.1,157.6,155.5,144.4,138.7,137.1,134.3,134.1,133.1,130.2,130.1,129.4,129.2,129.1,1 28.8,128.7,128.5,127.5,126.8,126.3,126.0,125.7,125.4,125.2,124.5,113.4,97.7,93.1,92.8.HRMS(ESI)m / z:(M+H) + Calculated for C 41 H 27 INO + 676.1132; Found 676.1163.

[0154] Example 9

[0155] Synthesis of compound 9:

[0156]

[0157] The substrate (0.1 mmol), furan derivative (166 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to give a white solid 9 (43.3 mg, 63%).

[0158] The characterization results of compound 9 are as follows:

[0159] 1 H NMR(400MHz,(CD3)2CO)δ8.20–8.39(m,2H),7.93–8.15(m,5H),7.69–7.91(m ,3H),7.66(s,1H),7.18–7.60(m,9H),6.63–6.73(m,1H),6.35–6.60(m,1H). 13 C NMR(100MHz,(CD3)2CO)δ145.3,143.4,141.7,139.5,138.2,130.3,129.8,129.6,129.2,128 .0,127.8,126.9,125.6,125.1,124.8,123.8,112.6,97.7,91.3,79.0.HRMS(ESI)m / z:(M+H) + Calculated for C 37 H 23INOS2 + 688.0260; Found 688.0291.

[0160] Example 10

[0161] Synthesis of compound 10:

[0162]

[0163] The substrate (0.1 mmol), furan derivative (116 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green liquid 10 (31.8 mg, 54%).

[0164] The characterization results of compound 10 are as follows:

[0165] 1 H NMR (500MHz, (CD3)2CO) δ8.00–8.21(m,2H),7.63–7.98(m,5H),7.34–7.61(m,6H),7.09–7.24(m,2H),6.87–7.04(m,H). 13 C NMR(125MHz,(CD3)2CO)δ145.8,145.2,144.3,139.8,137.2,136.7,130.9,129.9,129 .8,129.3,127.9,127.7,127.6,126.2,125.2,112.3,98.3,91.0.HRMS(ESI)m / z:(M+H) + Calculated for C 29 H 19 INOS2 + 587.9947; Found 588.0032. Example 11

[0166] Synthesis of compound 11:

[0167]

[0168] The substrate (0.1 mmol), furan derivative (116 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the solid was separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green solid 11 (36.5 mg, 62%).

[0169] The characterization results of compound 11 are as follows:

[0170] 1 H NMR (500MHz, (CD3)2CO) δ8.00–8.31(m,2H),7.65–7.98(m,5H),7.36–7.59(m,4H),7.35–6.82(m,6H),6.71(s,1H). 13 C NMR(125MHz,(CD3)2CO)δ164.8,162.8,155.7,154.7,146.5,146.2,145.9,144.0,141.0,140.2,139.6,137 .2,131.0,129.9,129.3,128.9,128.5,128.3,128.0,127.1,112.5,98.4,91.1,88.4.HRMS(ESI)m / z:(M+H) + Calculated for C 29 H 19 INOS2 + 587.9947; Found 587.9993.

[0171] Example 12

[0172] Synthesis of compound 12:

[0173]

[0174] The substrate (0.1 mmol), tetraphenylfuran (186 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness and separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green solid 12 (52.3 mg, 72%).

[0175] The characterization results of compound 12 are as follows:

[0176] 1 H NMR (500MHz, CDCl3) δ7.62–8.22(m,6H),7.35–7.54(m,6H),6.95–7.30(m,8H),6.69–6.92(m,9H),6.20–6.65(m,1H). 13C NMR (125MHz, CDCl3) δ163.1,154.9,153.4,152.2,150.6,143.0,142.1,139.0,138.8,133.4,130.9,123.0,129.7,129.2 ,129.0,128.7,128.6,128.0,127.9,127.7,127.4,127.3,127.1,126.9,126.7,113.0,97.8,93.8.HRMS(ESI)m / z:(M+H) + Calculated for C 45 H 31 INO + 727.1372; Found 727.1390.

[0177] Example 13

[0178] Synthesis of compound 13:

[0179]

[0180] The substrate (0.1 mmol), tetraphenylfuran derivative (254 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to give a white solid 13 (57.0 mg, 66%).

[0181] The characterization results of compound 13 are as follows:

[0182] 1 H NMR (500MHz, CDCl3) δ7.75–8.16(m,4H),7.36–7.65(m,8H),7.02–7.28(m,4H),6.63–6.98(m,9H),6.23–6.59(m,1H). 13 C NMR (125MHz, CDCl3) δ162.0,155.3,154.4,152.5,150.2,142.1,141.9,141.5,139.8,139.2,139.0,138.8,135.5,133.8,133.4,131.3 ,130.9,130.7,129.5,129.0,128.8,128.7,128.6,128.2,127.6,127.2,126.9,124.3,123.6,112.6,97.8,93.4.HRMS(ESI)m / z:(M+H) +Calculated for C 45 H 27 Cl4INO + 863.9886; Found 863.9833.

[0183] Example 14

[0184] Synthesis of compound 14:

[0185]

[0186] The substrate (0.1 mmol), tetraphenylfuran derivative (222 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 20 / 1) to obtain white body 14 (59.2 mg, 74%).

[0187] The characterization results of compound 14 are as follows:

[0188] 1 H NMR (500MHz, CDCl3) δ7.78–8.29(m,4H),7.42–7.71(m,5H),7.11–7.36(m,4H),6.12–7.06(m,13H). 13 C NMR (125MHz, CDCl3) δ164.1,163.5,162.9,162.4,162.2,161.6,161.0,155.2,154.2,152.4,151.1,150.1,143.4,142.2,138.9 ,131.9,131.7,129.5,129.0,128.8,128.8,127.6,115.9,115.7,115.5,115.30,113.8,99.4,97.8,93.5.HRMS(ESI)m / z:(M+H) + Calculated for C 45 H 27 F4INO + 800.1068; Found 800.1088.

[0189] Example 15

[0190] Synthesis of compound 15:

[0191]

[0192] The substrate (0.1 mmol), tetraphenylfuran (246 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness and separated by column chromatography (PE / EA = 20 / 1) to obtain a pale green solid 15 (56.0 mg, 66%).

[0193] The characterization results of compound 15 are as follows:

[0194] 1 H NMR (400MHz, CDCl3) δ8.08–8.15(m,2H),7.69–8.01(m,2H),7.37–7.62(m,5H),6.50–7.08(m,15H),6.30–6.44(m,2H),3.65–3.87(m,12H). 13 C NMR (100MHz, CDCl3) δ163.2,160.0,159.0,158.5,158.4,154.7,143.5,139.3,138.8,131.5,129.1,128.7,1 28.6,127.6,126.9,125.8,114.0,113.6,113.4,112.9,112.2,93.5,55.3,55.1,55.0.HRMS(ESI)m / z:(M+H) + Calculated for C 49 H 39 INO5 + 848.1867; Found 848.1913.

[0195] Example 16

[0196] Synthesis of compound 16:

[0197]

[0198] The substrate (0.1 mmol), furan derivative (140 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 16 (37.6 mg, 65%).

[0199] The characterization results of compound 16 are as follows:

[0200] 1H NMR (500MHz, (CD3)2CO) δ8.14–8.43(m,1H),7.58–8.06(m,3H),7.33–7.46(m,3H),6.74–7.07(m,7H),6.57–6.68(m,1H),3.85(s,3H),3.73(s,3H). 13 C NMR(125MHz,(CD3)2CO)δ160.5,159.7,157.1,155.1,148.7,146.9,145.8,145.0,138.1,130.0,129.3,12 4.0,120.3,120.3,114.6,114.5,113.8,113.8,113.7,95.2,93.1,79.0,55.5,55.3.HRMS(ESI)m / z:(M+H) + Calculated for C 29 H 22 FINO3 + 578.0623; Found 578.0608.

[0201] Example 17

[0202] Synthesis of compound 17:

[0203]

[0204] The substrate (0.1 mmol), furan derivative (168 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 17 (47.6 mg, 75%).

[0205] The characterization results of compound 17 are as follows:

[0206] 1 H NMR (500MHz, CDCl3) δ7.32–8.34(m,7H),7.14–6.65(m,3H),6.37–6.62(m,2 H),3.83(s,3H),3.74(s,3H),2.38(s,3H),2.06–2.29(m,6H),1.94(s,3H). 13C NMR (125MHz, CDCl3) δ157.6,157.2,156.9,154.9,144.6,137.6,136.9,136.3,133.8,127.2,126.1,125.9,12 5.8,125.6,122.6,114.5,107.0,106.4,94.5,92.7,55.5,55.4,17.6,17.6,11.9,11.6.HRMS(ESI)m / z:(M+H) + Calculated for C 33 H 30 FINO3+634.1249;Found 634.1263.

[0207] Example 18

[0208] Synthesis of compound 18:

[0209]

[0210] The substrate (0.1 mmol), furan derivative (128 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green liquid 18 (42.7 mg, 77%).

[0211] The characterization results of compound 18 are as follows:

[0212] 1 H NMR (500MHz, CDCl3) δ8.28(s,1H),7.89(d,J=8.0,1H),7.58–7.83(m,3H),7.48(d,J=5.2Hz ,1H),7.36(dd,J=8.0,5.6Hz,2H),7.10–7.22(m,2H),6.88–7.09(m,1H),6.67–6.83(m,4H). 13 C NMR (125MHz, CDCl3) δ164.0,163.2,162.1,161.2,159.0,156.7,154.7,147.8,146.5,145.4,144.1,135.9,132.5,1 30.8,130.8,129.6,129.6,129.6,129.5,123.1,115.5,115.3,114.7,114.5,95.9,94.1,92.4.HRMS(ESI)m / z:(M+H) +Calculated for C 27 H 16 F3INO + 554.0223; Found 554.0266.

[0213] Example 19

[0214] Synthesis of compound 19:

[0215]

[0216] The substrate (0.1 mmol), furan derivative (160 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 19 (40.2 mg, 65%).

[0217] The characterization results of compound 19 are as follows:

[0218] 1 H NMR (500MHz, CDCl3) δ8.15–8.41(m,3H),8.03(d,J=7.0Hz,1H),7.82–7.97(m,4H),7.66(d,J=8.0Hz,1H), 7.50–7.59(m,5H),7.35–7.50(m,2H),7.21–7.30(m,2H),6.99(s,1H),6.76(t,J=8.5Hz,1H),6.33(s,1H). 13 C NMR (125MHz, CDCl3) δ156.9,154.9,146.8,145.1,144.4,136.3,134.1,133.8,131.4,131.2,131.1,129.8,128.8 ,128.0,127.2,126.7,125.9,125.8,125.6,125.6,125.5,125.0,124.1,122.5,94.8,92.8.HRMS(ESI)m / z:(M+H) + Calculated for C 35 H 22 FINO + 618.0725; Found 618.0722.

[0219] Example 20

[0220] Synthesis of compound 20:

[0221]

[0222] The substrate (0.1 mmol), furan derivative (166 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 10 / 1) to obtain a white solid 20 (34.0 mg, 54%).

[0223] The characterization results of compound 20 are as follows:

[0224] 1 H NMR (500MHz, DMSO-d6) δ8.36(s,1H),7.78–8.23(m,6H),7.55–7.77(m,3H),7.29–7.46(m,2H),7.12–7.27(m,2H),6.75–7.09(m,2H),6.55(s,1H). 13 C NMR(125MHz,DMSO-d6)δ155.8,153.8,148.4,145.2,140.1,139.3,137.7,136.7,132.2,129.8,128.4,1 28.0,124.7,124.5,124.3,124.2,123.2,123.1,123.1,122.2,113.9,91.2,88.6.HRMS(ESI)m / z:(M+H) + Calculated for C 31 H 18 FINOS2 + 629.98530; Found 629.9857.

[0225] Example 21

[0226] Synthesis of compound 21:

[0227]

[0228] The substrate (0.1 mmol), furan derivative (116 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the solid was separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 21 (29.7 mg, 56%).

[0229] The characterization results of compound 21 are as follows:

[0230] 1 H NMR(400MHz, CDCl3) δ8.32(d,J=4.8Hz,1H),7.92(d,J=7.6Hz,1H),7.68(s,1H), 7.34–7.46(m,3H),7.27(d,J=7.2Hz,2H),6.87–6.96(m,3H),6.69–6.83(m,2H). 13 CNMR (100MHz, CDCl3) δ158.8,156.8,154.3,147.9,145.4,144.9,136.0,129.0,1 27.5,126.9,126.0,125.0,124.7,124.3,123.1,90.9,88.9.HRMS(ESI)m / z:(M+H) + Calculated for C 23 H 14 FINOS2 + 529.9540; Found 529.9598.

[0231] Example 22

[0232] Synthesis of compound 22:

[0233]

[0234] The substrate (0.1 mmol), furan derivative (116 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the solid was separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 22 (33.9 mg, 64%).

[0235] The characterization results of compound 22 are as follows:

[0236] 1 H NMR (500MHz, DMSO-d6) δ8.29(s,1H),7.52–8.17(m,5H),6.76–7.43(m,6H),6.58–6.74(m,1H). 13C NMR (125MHz, DMSO-d6) δ157.8,155.7,154.3,153.7,147.9,147.7,146.5,145.4,144.0,137.1,136.6,135.5,132 .5,130.6,128.3,128.1,127.6,127.2,126.9,126.3,123.5,123.5,114.3,95.9,90.5,88.5.HRMS(ESI)m / z:(M+H) + Calculated for C23H14FINOS2+

[0237] 529.9540; Found 529.9549.

[0238] Example 23

[0239] Synthesis of compound 23:

[0240]

[0241] The substrate (0.1 mmol), tetraphenylfuran (186 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness and separated by column chromatography (PE / EA = 10 / 1) to give a pale green solid 23 (52.3 mg, 78%).

[0242] The characterization results of compound 23 are as follows:

[0243] 1 H NMR (500MHz, CDCl3) δ7.56–8.42(m,4H),7.21–7.49(m,7H),6.88–7.17(m,9H),6.56–6.83(m,5H). 13 C NMR (125MHz, CDCl3) δ159.5,158.4,156.2,156.0,154.3,154.1,153.8,152.8,151.9,147.1,146.1,135.6,134.5,133.8,133.7 ,132.9,130.6,130.0,128.8,128.0,127.9,127.8,127.6,127.1,126.7,123.2,115.1,114.9,94.8,94.3.HRMS(ESI)m / z:(M+H) + Calculated for C 39 H 26 FINO+ 670.1038; Found 670.1089.

[0244] Example 24

[0245] Synthesis of compound 24:

[0246]

[0247] The substrate (0.1 mmol), tetraphenylfuran derivative (254 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the product was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 24 (58.8 mg, 73%).

[0248] The characterization results of compound 24 are as follows:

[0249] 1 H NMR (500MHz, CDCl3) δ7.68–8.44(m,2H),7.42–7.56(m,2H),7.20–7.38(m,5H),6.89–7.13(m,5H),6.74–6.86(m,5H),6.58–6.72(m,2H). 13 C NMR (125MHz, CDCl3) δ159.2,156.1,154.2,153.6,152.9,147.5,146.1,135.2,134.7,134.2,133.6,131.8 ,131.7,131.3,128.6,128.5,128.4,128.3,127.0,123.5,115.5,115.3,94.3,93.7.HRMS(ESI)m / z:(M+H) + Calculated for C 39 H 22 Cl4FINO + 805.94787; Found 805.9532.

[0250] Example 25

[0251] Synthesis of Compound 25

[0252]

[0253] The substrate (0.1 mmol), tetraphenylfuran (186 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness and separated by column chromatography (PE / EA = 10 / 1) to give a white solid 25 (50.5 mg, 68%).

[0254] The characterization results of compound 25 are as follows:

[0255] 1 H NMR (500MHz, CDCl3) δ7.66–8.40(m,2H),7.46–7.63(m,2H),6.85–7.19(m,10H),6.60–6.83(m,5H),6.45–6.54(m,2H). 13 C NMR (125MHz, CDCl3) δ164.0,163.5,162.9,162.6,162.0,161.5,160.9,1 60.6,159.5,156.2,155.4,154.2,153.2,151.9,150.4,147.4,146.1,13 2.4,131.6,129.32,129.3,129.2,129.2,128.8,128.7,123.4,115.4,11 5.2,115.2,115.0,113.8,113.6,97.2,94.2,93.6.HRMS(ESI)m / z:(M+H) + Calculated for C 39 H 22 F5INO + 742.0661; Found 742.0745.

[0256] Example 26

[0257] Synthesis of Compound 26

[0258]

[0259] The substrate (0.1 mmol), tetraphenylfuran derivative (246 mg, 0.5 mmol), and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the solid was separated by column chromatography (PE / EA = 10 / 1) to give a pale green solid 26 (59.3 mg, 75%).

[0260] The characterization results of compound 26 are as follows:

[0261] 1 H NMR (400MHz, CDCl3) δ7.63–8.36(m,2H),7.42–7.58(m,2H),6.75–7.14(m,10H),6.52–6.72(m,5H),6.26–6.41(m,2H),3.64–3.85(m,12H). 13 C NMR (100MHz, CDCl3)δ

[0262] 159.8,158.9,158.4,158.0,156.4,153.9,147.3,145.9,133.0,132.1,131.3,128.4,126.4, 123.0,114.8,113.4,113.4,113.3,112.2,94.2,93.8,55.2,55.1,55.0.HRMS(ESI)m / z:(M+H) +

[0263] Calculated for C 43 H 34 FINO5 + 790.1460; Found 790.1570.

[0264] Example 27

[0265] Synthesis of Compound 27

[0266]

[0267] The substrate (0.05 mmol) was added to the reaction tube, with toluene as the solvent, followed by LDA (0.15 mL, 1 mmol / mL). The reaction was allowed to proceed for 30 min until complete. The reaction was quenched with saturated ammonium chloride aqueous solution (10 mL), extracted three times with EA, and the organic phase was evaporated to dryness. The mixture was then separated by column chromatography (PE / EA = 10 / 1) to give a white solid 27 (19.0 mg, 75%).

[0268] The characterization results of compound 27 are as follows:

[0269] 1H NMR (500MHz, CDCl3) δ8.29(d,J=5.0Hz,1H),7.72(dd,J=8.0,3.5Hz,1H),7.60(d,J=8.5Hz,1H),7.56(d,J=5.5Hz,1H),7.31(d,J=5.5Hz,1H),7.19–7 .27(m,2H),7.05(d,J=7.5Hz,1H),6.83(d,J=8.5Hz,1H),6.71–6.67(m,1H ),3.84–3.90(m,6H),2.38(s,3H),2.24(s,3H),1.92(s,3H),1.67(s,3H). 13 C NMR (125MHz, CDCl3) δ158.0,157.7,155.7,152.13,147.8,145.7,143.9,142.0,138.4,138.2,137.7,135.4,135.0,134.9,126.6,126 .0,124.8,122.6,116.1,115.9,114.0,107.2,95.4,95.4,91.2,89.9,55.5,55.2,54.6,17.5,17.4,11.9,11.3.HRMS(ESI)m / z:(M+H) + Calculated for C 33 H 29 FNO3 + 506.2126; Found 506.2133.

[0270] Example 28

[0271] Synthesis of Compound 28

[0272]

[0273] The substrate (0.05 mmol) was added to the reaction tube, with toluene as the solvent, followed by LDA (0.15 mL, 1 mmol / mL). The reaction was allowed to proceed for 30 min until complete. The reaction was quenched with saturated ammonium chloride aqueous solution (10 mL), extracted three times with EA, and the organic phase was evaporated to dryness. The mixture was then separated by column chromatography (PE / EA = 10 / 1) to give a white solid 28 (15.2 mg, 62%).

[0274] The characterization results of compound 28 are as follows:

[0275] 1H NMR(500MHz, (CD3)2CO) δ8.41(dd,J=13.5,8.0Hz,2H),8.29(d,J=4.5Hz,1H),8.25(d,J=7.0Hz,1H),8.04–8.15(m,2H),7.73–7.82(m,2H),7.66– 7.72(m,1H),7.52–7.65(m,3H),7.43(d,J=5.0Hz,1H),7.38(d,J=7.0Hz ,1H),7.24–7.35(m,2H),6.79–6.94(m,3H),5.49(dd,J=6.0,1.5Hz,1H). 13 C NMR (125MHz, (CD3)2CO) δ158.3,156.9,156.3,152.8,148.7,148.6,147.5,147.4,146.2,145.6,145.5,140.2,139.3,135.3,131.2,131.1 ,129.7,127.2,126.9,126.7,126.7,125.9,125.3,125.2,125.2,124.6,118.8,116.8,116.6,96.0,92.5,53.1,51.8.HRMS(ESI)m / z:(M+H) + Calculated for C 35 H 21 FNO + 490.1602; Found 490.1673.

[0276] Example 29

[0277] Synthesis of Compound 29

[0278]

[0279] The substrate (0.05 mmol) was added to the reaction tube, with toluene as the solvent, followed by LDA (0.15 mL, 1 mmol / mL). The reaction was allowed to proceed for 30 min until complete. The reaction was quenched with saturated ammonium chloride aqueous solution (10 mL), extracted three times with EA, and the organic phase was evaporated to dryness. The mixture was then separated by column chromatography (PE / EA = 10 / 1) to give 29 g of pale green solid (11.7 mg, 58%).

[0280] The characterization results of compound 29 are as follows:

[0281] 1H NMR (500MHz, CDCl3) δ8.63(d,J=3.0Hz,1H),8.27(dd,J=9.0,4.5Hz,1H),8.15(d,J=6.5Hz,1H),7.69( s,1H),7.36–7.48(m,3H),7.20–7.35(m,3H),7.11(dd,J=5.0,2.5Hz,1H),6.85(td,J=8.5,2.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ157.5,156.6,155.5,154.2,152.5,148.4,147.8,146.5,143.3,138.6,137.1,135.8,135.3,13 4.9,134.8,129.3,129.2,127.8,127.4,127.0,126.3,124.7,122.4,115.9,115.8,90.3,88.1.HRMS(ESI)m / z:(M+H) + Calculated for C 23 H 13 FNOS2 + 402.0417; Found 402.0415.

[0282] Example 30

[0283] Synthesis of Compound 30

[0284]

[0285] Add high-iodide substrate (0.5 mmol), tetraphenylfuran (0.94 g, 2.5 mmol), and tBuOK (170 mg, 1.5 mmol) to the reaction tube. Use DCM (1 mL) as solvent and react at room temperature for 12 h. After the reaction is complete, evaporate the solvent to dryness and separate by column chromatography (PE / EA = 10 / 1) to obtain 2x. Then, add 0.2 mmol of 2x as substrate to the reaction tube, along with 1,3-diphenylisobenzofuran (540 mg, 2.0 mmol), and use toluene (2 mL). Using LDA (0.6 mL, 0.6 mmol / mL) as a solvent, the reaction was carried out at room temperature for 30 min. After the reaction was completed, the reaction tube was placed in an oil bath at 50 °C, and Et3SiH (116 mg, 1.0 mmol) and WCl6 (397 mg, 1.0 mmol) were added. The reaction was carried out for 2 h. After the reaction was completed, 20 mL of saturated NaHCO3 aqueous solution was added to quench the reaction. The mixture was extracted three times with DCM, the organic phase was evaporated to dryness, and separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 30 (74.3 mg, 43%).

[0286] The characterization results of compound 30 are as follows:

[0287] 1 H NMR (500MHz, CDCl3) δ8.08 (d, J = 6.0Hz, 1H), 6.53–7.94 (m, 38H), 6.43 (s, 1H). 13 CNMR (125MHz, CDCl3) δ197.0,161.3,144.7,143.2,142.9,140.8,140.4,139.5,139.1,1 38.6,138.3,138.1,137.0,136.7,134.7,132.8,132.4,132.1,132.0,131.8,131.5,131. 2,130.4,129.9,129.1,128.7,128.5,128.4,128.1,127.9,127.6,127.3,127.2,127.0, 126.7,126.5,126.4,125.6,125.5,124.0,120.8,118.7,100.0,70.6.HRMS(ESI)m / z:(M) + Calculated for C 60 H 41 F3NO2 + 864.3084; Found 864.3162.

[0288] Example 31

[0289] Synthesis of Compound 31

[0290]

[0291] The substrate (0.1 mmol), 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 31 (58.8 mg, 73%).

[0292] The characterization results of compound 31 are as follows:

[0293] 1H NMR (500MHz, CDCl3) δ8.19(d,J=4.0Hz,1H),7.95–8.02(m,3H),7.80(d,J=7.0Hz,1H),7.59–7.64(m,2H),7.53(d,J =7.0Hz,1H),7.41–7.50(m,3H),7.06–7.21(m,6H),6.72(d,J=8.5Hz,1H),6.60(dd,J=8.0,4.5Hz,1H),3.70(s,3H). 13 C NMR (125MHz, CDCl3) δ159.7,153.8,151.1,150.1,147.7,146.6,137.8,134.9,134.5,130.3,130.0,128.4,127.7,127 .6,125.6,125.6,123.6,122.5,121.2,110.5,96.0,92.1,91.4,55.6.IR(neat)1660,1267,1179,1006,938,741,636cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 32 H 23 INO2 + 580.0768; Found 580.0802.

[0294] Example 32

[0295] Synthesis of Compound 32

[0296]

[0297] The substrate (0.1 mmol), 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 32 (58.8 mg, 73%).

[0298] The characterization results of compound 32 are as follows:

[0299] 1H NMR(500MHz, CDCl3)δ8.24(d,J=4.0Hz,1H),7.97–8.03(m,3H),7.83(d,J=7.3Hz,1H),7.58–7.65(m, 3H),7.42–7.53(m,3H),7.08–7.26(m,6H),7.00(dd,J=8.5,1.5Hz,1H),6.66(dd,J=8.0,4.5Hz,1H). 13 C NMR (125MHz, CDCl3) δ158.8,149.7,149.4,147.8,146.8,143.3,142.4,134.1,133.4,130.4,129.3,129.0,128.4,128.1,128.1,127. 7,126.2,126.0,123.8,123.1,122.4,120.2(q,J=256.0Hz),119.4,95.5,92.1,91.4.IR(neat)1254,1210,1146,995,894,750,670cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 32 H 20 F3INO2 + 634.0485; Found 634.0491.

[0300] Example 33

[0301] Synthesis of Compound 33

[0302]

[0303] The substrate (0.1 mmol), 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) and tBuOK (34 mg, 0.3 mmol) were added to the reaction tube. DCM (1 mL) was used as the solvent, and the reaction was carried out at room temperature for 12 h. After the reaction was completed, the solvent was evaporated to dryness, and the mixture was separated by column chromatography (PE / EA = 10 / 1) to give a white solid 33 (58.8 mg, 73%).

[0304] The characterization results of compound 33 are as follows:

[0305] 1H NMR(500MHz, CDCl3)δ8.15–8.26(m,1H),7.92–8.03(m,3H),7.75–7.86(m,1H) ,7.41–7.65(m,6H),7.03–7.30(m,6H),6.76–6.86(m,1H),6.57–6.68(m,1H). 13 C NMR (125MHz, CDCl3) δ159.0,155.8(d,J=250.0Hz),150.6,149.2,147.8,146.7,134.3,133.7,131.9,130.9,130.8,128.9,128.8,128.3,128 .0,127.7,126.1,126.0,123.8,122.9,121.4,114.6(d,J=22.5Hz),95.8,92.5,90.9.IR(neat)2852,1415,1304,1246,1152,993,751,699cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 31 H 20 FINO2 + 568.0568; Found 568.0526.

[0306] Example 34

[0307] Synthesis of Compound 34

[0308]

[0309] Substrate (0.05 mmol) and 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) were added to the reaction tube. Toluene (1 mL) was used as solvent, and LDA (0.15 mL, 0.15 mmol / mL) was added. The reaction was carried out at room temperature for 1 h. After the reaction was completed, 1,3-diphenylisobenzofuran was rapidly separated using a neutral alumina column (PE / DCM = 4 / 1). The mixture in the column was then flushed out completely (DCM / MeOH = 10 / 1). After evaporation, the mixture was placed in an oil bath at 60 °C, and Et3SiH (29.0 mg, 0.25 mmol) and WCl6 (99.0 mg, 0.25 mmol) were added. The reaction was carried out for 2 h. After the reaction was completed, saturated NaHCO3 aqueous solution (20 mL) was added to quench the reaction. The mixture was extracted three times with DCM, and the organic phase was evaporated to dryness and separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 34 (16.9 mg, 49%).

[0310] The characterization results of compound 34 are as follows:

[0311] 1 H NMR(500MHz, CDCl3)δ8.10(d,J=6.0Hz,1H),7.69–7.78(m,2H),7.57–7.67(m ,5H),7.41–7.49(m,3H),7.38(d,J=8.0Hz,1H),7.30–7.36(m,2H),7.14–7.2 3(m,4H),7.01–7.12(m,4H),6.88–6.99(m,3H),6.76(d,J=7.5Hz,1H),6.59( d,J=7.5Hz,1H),6.42–6.52(m,4H),6.35(td,J=7.5,1.5Hz,1H),3.39(s,3H). 13 C NMR (125MHz, CDCl3) δ164.0,157.4,144.4,139.2,138.5,138.5,138.0,136.8136.34136.1,132.7,132.4, 131.9,131.9,131.8,131.6,131.5,131.3,131.0,130.8,130.3,130.3,129.8,129.6,129.0,128.6,128.5 ,127.9,127.8,127.4,127.3,127.0,126.8,126.5,126.5,126.5,126.4,125.9,125.8,125.5,125.2,125. 0,124.9,124.6,124.4,124.4,123.3,118.3,103.9,55.5.IR(neat)2360,1273,1157,1072,999,742,696cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 52 H 36 NO + 690.2791; Found 690.2797.

[0312] Example 35

[0313] Synthesis of Compound 35

[0314]

[0315] Substrate (0.05 mmol) and 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) were added to the reaction tube. Toluene (1 mL) was used as solvent, and LDA (0.15 mL, 0.15 mmol / mL) was added. The reaction was carried out at room temperature for 1 h. After the reaction was completed, 1,3-diphenylisobenzofuran was rapidly separated using a neutral alumina column (PE / DCM = 4 / 1). The mixture in the column was then flushed out completely (DCM / MeOH = 10 / 1). After evaporation, the mixture was placed in an oil bath at 60 °C, and Et3SiH (29.0 mg, 0.25 mmol) and WCl6 (99.0 mg, 0.25 mmol) were added. The reaction was carried out for 2 h. After the reaction was completed, saturated NaHCO3 aqueous solution (20 mL) was added to quench the reaction. The mixture was extracted three times with DCM, and the organic phase was evaporated to dryness and separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 35 (21.2 mg, 57%).

[0316] The characterization results of compound 35 are as follows:

[0317] 1 H NMR(500MHz, CDCl3)δ8.12(d,J=6.0Hz,1H),7.75–7.78(m,1H),7.69–7.73(m,1H) ),7.60–7.68(m,5H),7.44–7.53(m,3H),7.34–7.38(m,2H),7.30–7.33(m,1H),7. 17–7.26(m,4H),7.03–7.25(m,5H),6.91–7.00(m,3H),6.73(d,J=7.3Hz,1H),6. 68(d,J=7.5Hz,1H),6.56(d,J=7.6Hz,1H),6.45–6.52(m,2H),6.29–6.34(m,1H). 13C NMR (125MHz, CDCl3) δ163.0,145.5,142.0,140.7,138.7,138.3,138.0,138.0,137.2,137.0,135.4,132. 8,132.0,131.9,131.7,131.6,131.5,131.4,131.0,130.5,130.4,130.2,130.0,129.8,129.8,128.7,128 .6,127.9,127.8,127.7,127.6,127.3,127.1,127.0,126.7,126.7,126.6,126.2,125.6,125.5,125.4,1 24.9,124.8,124.5,123.3,121.0,119.0,118.9,115.2.IR(neat)2360,1247,1211,1152,1115,762,699cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 52 H 33 F3NO + 744.2509; Found 744.2491. Example 36

[0318] Synthesis of Compound 36

[0319]

[0320] Substrate (0.05 mmol) and 1,3-diphenylisobenzofuran (136 mg, 0.5 mmol) were added to the reaction tube. Toluene (1 mL) was used as solvent, and LDA (0.15 mL, 0.15 mmol / mL) was added. The reaction was carried out at room temperature for 1 h. After the reaction was completed, 1,3-diphenylisobenzofuran was rapidly separated using a neutral alumina column (PE / DCM = 4 / 1). The mixture in the column was then flushed out completely (DCM / MeOH = 10 / 1). After evaporation, the mixture was placed in an oil bath at 60 °C, and Et3SiH (29.0 mg, 0.25 mmol) and WCl6 (99.0 mg, 0.25 mmol) were added. The reaction was carried out for 2 h. After the reaction was completed, saturated NaHCO3 aqueous solution (20 mL) was added to quench the reaction. The mixture was extracted three times with DCM, and the organic phase was evaporated to dryness and separated by column chromatography (PE / EA = 10 / 1) to obtain a pale green solid 36 (18.3 mg, 54%).

[0321] The characterization results of compound 36 are as follows:

[0322] 1H NMR(500MHz, CDCl3)δ8.12(d,J=6.0Hz,1H),7.50–7.77(m,10H),7.28–7.40(m,4H),7.08–7.26(m,7H), 6.93–7.00(m,3H),6.74–6.83(m,2H),6.62(d,J=7.5Hz,1H),6.45–6.55(m,3H),6.35(t,J=7.3Hz,1H). 13 C NMR(125MHz, CDCl3) δ163.1,159.4(d,J=257.5Hz),142.0,141.9,138.9,138.3,137.9,137.0,136.8,136.8,134.8, 132.6,132.0,131.9,131.6,131.5,131.5,131.4,131.3,131.0,130.1,130.1,129.7,129.3,129.3,128.7,128.5,12 7.9,127.8,127.7,127.5,127.4,127.0,126.9,126.8,126.8,126.6,126.6,126.2,126.2,125.5,125.4,125.2,124 .8,124.6,124.5,121.1(d,J=8.8Hz),118.8,109.0(d,J=22.5Hz).IR(neat)2856,1382,1214,1104,1031,744,695cm -1 .HRMS(ESI)m / z:(M+H) + Calculated for C 51 H 33 FN + 678.2592; Found 678.2521.

[0323] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0324] As used in this invention, the term "comprising" is an open-ended expression, meaning it includes the contents specified in this invention but does not exclude other aspects.

[0325] As used in this invention, the term "and / or" includes any one or more of the associated listed items and all combinations thereof. Although embodiments of this description have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of this description, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing a nitrogen-containing heterocyclic polyaromatic compound with axial chirality, characterized in that, The method includes the following steps: Step (1): Using diarylcyclic pyridine highiodide salt as raw material, pyridineyne or benzyne intermediate 1 is obtained under the action of alkali and solvent; Step (2): Under the action of alkali and solvent, the pyridyne or benzyne intermediate 1 undergoes a rapid [4+2] cycloaddition reaction with the polyaromatic ring substituted diene to obtain the product; Step (3): In a solvent, the product obtained in step (2) can be further hydrogenated under the action of an alkali to generate a second pyridyne or benzene intermediate 2; Step (4): The pyridyne or benzyne intermediate 2 obtained in step (3) is further reacted with a polycyclic substituted diene in a [4+2] cycloaddition reaction to rapidly obtain an aza-polycyclic compound. The reaction process of the method is shown in Equation A below: Among them, R 1 R 2 R 3 R 4 R 5 Each of the following is independently selected from one or more of hydrogen, alkyl, trifluoromethyl, trifluoromethoxy, aryl, silyl, and halogen; R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 Each of the following can be independently hydrogen, alkyl, or aryl.

2. The method as described in claim 1, characterized in that, In step (1), the base is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA; and / or, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether; and / or, based on diarylcyclic pyridine periodic salt, the volume of the solvent used is 0.5-10 mL; and / or, the molar ratio of diarylcyclic pyridine periodic salt to base is 1:1-5; and / or, the reaction temperature is 0-80℃. And / or, in step (2), the base is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA; and / or, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether; and / or, the molar ratio of the pyridyne or benzyne intermediate 1, the polyaromatic substituted diene, and the base is 1:1-5:1-5; and / or, the reaction temperature is 0-80℃.

3. The method as described in claim 1, characterized in that, In step (3), the base is one or more of K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA; and / or, the solvent is one or more of methanol, ethanol, tetrahydrofuran, toluene, acetonitrile, ethyl acetate, dioxane, dichloromethane, diethyl ether, and petroleum ether; and / or, the molar ratio of the product to the base is 1:1-5; and / or, the reaction temperature is 0-80℃. And / or, in step (4), the molar ratio of the pyridyne or benzyne intermediate 2 to the polycyclic substituted diene is 1:1-5:1-5; and / or, the reaction temperature is 0-80℃.

4. The method as described in claim 1, characterized in that, The method for synthesizing the diaryl cyclic pyridine periodic salt is as follows: Step (1): Using substituted 2-halo-3-aminopyridine as a raw material, under the conditions of Pd catalyst, solvent, base and ligand, it undergoes Suzuki coupling reaction with polysubstituted arylboronic acid to obtain intermediate 1; Step (2): The intermediate 1 obtained in step (1) is subjected to diazotization in the presence of acid, additives and solvent to replace the amino group with iodine to obtain intermediate 2; Step (3): The intermediate 2 obtained in step (2) is oxidized in the presence of acid, oxidant, and solvent to obtain diarylpyridine periodic salt; the reaction equation is shown below: R contains R 4 R 5 R' contains R 1 R 2 R 3 X is a halogen; where R 1 R 2 R 3 R 4 R 5 The definition is the same as in claim 1.

5. The method as described in claim 4, characterized in that, In step (1), the Pd catalyst is one or more of Pd(OAc)2, Pd(dba)2, Pd2(dba)3, Pd(Ph3P)4, PdCl2, and Pd(MeCN)2Cl2; and / or, the ligand is one or more of Dave-Phos, X-Phos, S-Phos, Ph3P, (Ph2P)2(CH2)2, (Ph2P)2(CH2)3, (Ph2P)2(CH2)4, and tBu-Phos; and the solvent is PhMe, MeOH, or E. One or more of tOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, and DMF; and / or, the base is one or more of Na2CO3, K2CO3, NaOH, KOH, tBuOLi, tBuONa, tBuOK, LiHMDS, and LDA; and / or, the reaction temperature is room temperature - 120°C; and / or, the molar ratio of the substituted 2-halo-3-aminopyridine, the base, the Pd catalyst, and the ligand is 1:1-10:0.01-1:0.01-1; And / or, in step (2), the acid is one or more of H2SO4, HCl, TFA, TfOH, TsOH, HBF4; and / or, the additive is one or more of NaNO2, KNO2, tBuONO; the solvent is one or more of PhMe, MeOH, EtOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, DMF; and / or, the iodine source used is one or more of NaI, I2, KI, TBAI; and / or, the reaction temperature is -80–100℃; and / or, the molar ratio of intermediate 1, acid, additive, and iodine source is 1:1-10:0.5-2:0.5-2; And / or, in step (3), the oxidant is one or more of H2O2, m-CPBA, and NaIO4; and / or, the acid is one or more of H2SO4, HCl, TFA, TfOH, TsOH, and HBF4; and / or, the solvent is one or more of PhMe, MeOH, EtOH, H2O, THF, dioxane, EtOAc, MeCN, DCM, and DMF; and / or, the reaction temperature is -80–100℃; and / or, the molar ratio of intermediate 2, acid, and oxidant is 1:1–10:1–5.

6. The method as described in claim 1, characterized in that, In step (2), the structural formula of the product includes the following: And / or, the polycyclic aromatic compounds obtained in step (4) have the following structural formulas: Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is one or more of hydrogen, alkyl, and aryl groups.

7. The method as described in claim 1, characterized in that, The polycyclic aromatic compound is subjected to a one-step de-double-bridged epoxide aromatization to obtain a polycyclic aromatic hydrocarbon compound, the structural formula of which includes the following: Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is one or more of hydrogen, alkyl, and aryl groups.

8. A nitrogen-containing polycyclic aromatic hydrocarbon compound, characterized in that, Its structure is shown in Equation 1 below: R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 It is one or more of hydrogen, alkyl, and aryl groups.

9. The azahexacyclic aromatic hydrocarbon compound as described in claim 8, characterized in that, Its structure is as follows:

10. The use of the nitrogen-containing polycyclic aromatic hydrocarbon compound as described in claim 8 in electrodes, optoelectronic devices, and fluorescence-based materials.

Images