Method for synthesizing pyridine, bipyridine and terpyridine ligands

文档序号：460882 发布日期：2021-12-31 浏览：23次中文

阅读说明：本技术 一种合成吡啶、联吡啶、三联吡啶配体的方法 (Method for synthesizing pyridine, bipyridine and terpyridine ligands ) 是由舒伟任玉峰于 2021-10-08 设计创作，主要内容包括：一种合成吡啶、联吡啶、三联吡啶配体的方法,所述方法采用光敏剂和钴肟复合物作为催化剂,具有安全、温和、高效和经济的有益效果。同时,钴肟复合物催化剂对水、氧不敏感,对反应要求不高,可大大降低操作难度。(The method for synthesizing the pyridine, bipyridine and terpyridine ligands adopts a photosensitizer and a cobalt oxime compound as catalysts, and has the advantages of safety, mildness, high efficiency and economy. Meanwhile, the cobalt oxime compound catalyst is insensitive to water and oxygen, has low requirement on reaction and can greatly reduce the operation difficulty.)

1. A method for synthesizing a compound of formula II, comprising:

in the presence of a catalyst and illumination and under the condition of adding acid and/or alkali and under the protection of inert gas, reacting a compound shown as a formula I with an ammonium source in a solvent, and carrying out aftertreatment to obtain a compound shown as a formula II; wherein the content of the first and second substances,

the catalyst comprises a photosensitizer and a cobalt oxime complex;

R₁including groups selected from C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C9-C20 polycyclic aryl, substituted or unsubstituted C6-C20 heteroaryl, substituted or unsubstituted C3-C10 heterocyclyl, substituted or unsubstituted C3-C10 cycloalkyl, and substituted or unsubstituted C3-C10 cycloalkenyl;

R₂comprises a heterocyclic group selected from C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl and substituted or unsubstituted C3-C10;

R₃comprises a heterocyclic group selected from a hydrogen atom, a C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 heteroaryl group and a substituted or unsubstituted C3-C10 heterocyclic group;

R₄comprises a hydrogen atom, a C1-C10 alkyl group, an ester group, a substituted or unsubstituted C6-C20 aryl group, a carbonyl group and a cyano group; or

R₁、R₄Together with the atoms to which they are attached form substituted or unsubstitutedA C3-C10 carbocyclic ring, a substituted or unsubstituted C3-C10 heterocyclic ring, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C9-C20 polycyclic aryl group.

2. The method of claim 1, the photosensitizer comprising at least one selected from the following structures:

3. the method of any one of claims 1-2, wherein the cobalt oxime complex comprises at least one selected from the following structures:

4. the method of any of claims 1-3, the ammonium source comprising at least one selected from the group consisting of ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium chloride, ammonium fluoroborate, ammonium fluoride, ammonium formate, and ammonium acetate; preferably, the ammonium source is ammonium acetate.

5. The method of any one of claims 1-3, the acid comprising a compound selected from the group consisting of trifluoroacetic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, scandium triflate, and yttrium triflate; preferably, the acid is scandium triflate; and/or

The base comprises at least one selected from sodium acetate and triethylene diamine; preferably, the base is triethylene diamine; and/or

The solvent includes at least one selected from acetonitrile, dichloromethane, toluene, dioxane, dichloroethane and tetrahydrofuran, preferably acetonitrile.

6. The process according to any one of claims 1 to 5, wherein the compound of formula I is fed in a molar ratio to the ammonium source of from 1: 1 to 1: 10; and/or the feeding molar ratio of the acid to the compound shown in the formula I is 5: 100-50: 100; and/or the feeding molar ratio of the compound shown in the formula I to the alkali is 1: 0.5-1: 3; and/or the feeding molar ratio of the photosensitizer to the compound shown in the formula I is 0.5: 100-10: 100; and/or the feeding molar ratio of the cobalt oxime compound to the compound shown in the formula I is 0.5: 100-10: 100; and/or the volume ratio of the substance of the compound shown in the formula I to the solvent is 0.01 mmol: 1mL-0.2 mmol: 1 mL.

7. The method according to any one of claims 1-6, wherein the illumination has a wavelength of 420nm-475 nm; and/or the reaction time is 12h-36 h; and/or the temperature of the reaction is between 10 ℃ and 40 ℃.

8. The method according to any one of claims 1-7, the post-processing comprising: diluting with water and ethyl acetate, extracting the water phase twice with ethyl acetate, mixing the extracted organic phases, washing with saturated sodium chloride, drying with anhydrous magnesium sulfate, and separating.

9. The method of any one of claims 1-8, wherein R is₁Including groups selected from methyl, phenyl, 4-tolyl, 4-methoxyphenyl, 2-pyridyl, 6-methyl-2-pyridyl, 3, 5-dimethylphenyl, indanyl, 3, 4-dihydro-2H-chromenyl, thiopyranyl, or the following c, d, e, f structures:

the R is₂Including groups selected from methyl, phenyl, 4-tolyl, 2-pyridyl, propyl, 6-methyl-2-pyridyl, 2-furyl, 5-methyl-2-thienyl, 3, 5-dimethylphenyl, 4-tert-butylphenyl and 4-nitrophenyl;

the R is₃Comprises a hydrogen atom, phenyl, methyl, 2-naphthyl, 4-chlorophenyl,N-methyl-2-pyrrolyl, 4-pyridyl, 3-thienyl, 2-thienyl, 4-methylphenyl, 4-tert-butylphenyl, 4-phenylphenyl and 2-furyl;

the R is₄Including a group selected from a hydrogen atom, a phenyl group, an ester group, a methyl group, a 4-methoxyphenyl group, a carbonyl group and a cyano group; or

R₁、R₄Together with the atoms to which they are attached form a substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted cycloheptenyl, phenyl, 4-tolyl, 4-methoxyphenyl, substituted or unsubstituted pyridyl, 3, 5-dimethylphenyl, 1H-indenyl, 1, 2-dihydronaphthyl, 2H-chromenyl, thiopyranyl;

or R₁、R₄Together with the atoms to which they are attached, form the following structure:

wherein the content of the first and second substances,represents a single bond, a carbon-oxygen double bond or a conjugated double bond; in the compounds of the formula I, p1 and p3 are indicatedOne of which represents a carbon-oxygen double bond and the other a single bond, p2Represents a single bond; in the compounds of the formula II, p1, p2 and p3 are indicatedForming a conjugated double bond structure.

10. Use of a photosensitizer comprising at least one member selected from the group consisting of the structures according to the method of claim 2 and a cobalt oxime complex for the preparation of a pyridine compound; the cobalt oxime complex comprising at least one selected from the group consisting of the structures in the method according to claim 3.

Technical Field

The invention belongs to the field of drug synthesis, and relates to a method for synthesizing pyridine, bipyridine and terpyridine ligands.

Background

Pyridine is a very common heterocyclic compound that is present in many natural products, such as nicotine, and nucleic acids, among others. In addition, the pyridine skeleton and its derivatives have wide pharmaceutical properties and pharmacological activities, and thus the pyridine skeleton is also an important component of many clinical drugs and is used in the treatment of various diseases, such as cancer, bacteria, oxidation, viruses, heart failure, various arthritis, and the like. In addition, pyridine skeleton and its derivatives have sigma electron donating ability and pi electron accepting ability, and thus are widely used as monodentate, bidentate and polydentate ligands to form stable metal chelates with ions of various metals (iron, cobalt, nickel, copper, ruthenium, etc.), and in the fields of catalytic materials, chemical analysis, luminescent materials, modification of biological cell molecules, probes, and the like.

Based on the chemical and biological activity of pyridines, scientists have developed a number of methods for synthesizing pyridine backbones. However, the currently reported methods for synthesizing pyridine compounds often have problems, such as insufficient universality, harsh reaction conditions, difficult availability of raw materials, more byproducts, and the like.

Patent application CN106632019A discloses a preparation method of polysubstituted pyridine, but the method requires dimethyl sulfoxide as solvent and oxidant, and the reaction is carried out at 85-95 ℃, which has certain dangers.

Therefore, there is a need to develop a green, efficient and mild method for preparing pyridine compounds.

Disclosure of Invention

In order to solve the problems, the invention provides a synthesis method of a pyridine compound and application of a photosensitizer and a cobalt oxime compound in preparation of the pyridine compound.

In a first aspect, the invention provides a synthesis method of a pyridine compound.

A method for synthesizing a compound of formula II, comprising:

the catalyst comprises a photosensitizer and a cobalt oxime complex;

R₁comprises a group selected from C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C9-C20 polycyclic aryl, substituted or unsubstituted C6-C20 heteroaryl, substituted or unsubstituted C3-C10 heterocyclic group, and substituted or unsubstituted C3-C10 cycloalkyl and substituted or unsubstituted C3-C10 cycloalkenyl;

R₂comprises a heterocyclic group selected from C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl and substituted or unsubstituted C3-C10;

R₄comprises a hydrogen atom, a C1-C10 alkyl group, an ester group, a substituted or unsubstituted C6-C20 aryl group, a carbonyl group and a cyano group; or

R₁、R₄Together with the atoms to which they are attached form a substituted or unsubstituted C3-C10 carbocyclic ring, a substituted or unsubstituted C3-C10 heterocyclic ring, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C9-C20 polycyclic aryl group.

In some embodiments, the synthesis method adds both an acid and a base.

The inert gas comprises nitrogen, argon, helium, neon, argon, krypton or xenon; preferably nitrogen.

The photosensitizer comprises at least one selected from the following structures:

the cobalt oxime complex comprises at least one selected from the following structures:

the ammonium source includes at least one selected from the group consisting of ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium chloride, ammonium fluoroborate, ammonium fluoride, ammonium formate, and ammonium acetate. Preferably, the ammonium source is ammonium acetate.

The acid comprises a compound selected from the group consisting of trifluoroacetic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, scandium triflate, and yttrium triflate. Preferably, the acid is scandium triflate.

The base includes at least one selected from sodium acetate and triethylenediamine. Preferably, the base is triethylene diamine.

The solvent includes at least one selected from acetonitrile, dichloromethane, toluene, dioxane, dichloroethane and tetrahydrofuran, preferably acetonitrile.

The feeding molar ratio of the compound shown in the formula I to the ammonium source is 1: 1-1: 10. In some embodiments, the preferred molar ratio of the compound of formula I to the ammonium source is 1: 2.

The feeding molar ratio of the acid to the compound shown in the formula I is 5: 100-50: 100. In some embodiments, the preferred molar ratio of the acid to the compound of formula I is 10: 100 to 30: 100. In some embodiments, the preferred molar ratio of acid to compound of formula I is 20: 100.

The feeding molar ratio of the compound shown in the formula I to the alkali is 1: 0.5-1: 3. In some embodiments, the compound of formula I and the base are preferably fed in a molar ratio of 1: 1 to 1: 2. In some embodiments, the preferred molar ratio of the compound of formula I to the base is 1: 1.5.

The feeding molar ratio of the photosensitizer to the compound shown in the formula I is 0.5: 100-10: 100. In some embodiments, the preferred molar ratio of photosensitizer to compound of formula I is from 1: 100 to 5: 100. In some embodiments, the preferred molar ratio of photosensitizer to compound of formula I is from 2: 100 to 4: 100. In some embodiments, the preferred dosing mole ratio of the photosensitizer to the compound of formula I is 2: 100.

The feeding molar ratio of the cobalt oxime compound to the compound shown in the formula I is 0.5: 100-10: 100. In some embodiments, the cobalt oxime complex and the compound of formula I are preferably fed in a molar ratio of 1: 100 to 8: 100. In some embodiments, the cobalt oxime complex and the compound of formula I are preferably fed in a molar ratio of 2: 100 to 6: 100. In some embodiments, the cobalt oxime complex and the compound of formula I are preferably fed in a molar ratio of 3: 100 to 5: 100. In some embodiments, the cobalt oxime complex and the compound of formula I are preferably fed in a molar ratio of 4: 100.

The volume ratio of the substance of the compound shown in the formula I to the solvent is 0.01 mmol: 1mL-0.2 mmol: 1 mL. In some embodiments, a preferred ratio of the amount of said substance of the compound of formula I to the volume of solvent is from 0.05 mmol: 1mL to 0.15 mmol: 1 mL. In some embodiments, a preferred ratio of the amount of material of the compound of formula I to the volume of solvent is 0.1 mmol: 1 mL.

The wavelength of the illumination is 420nm-475 nm. In some embodiments, the illumination has a wavelength of 450nm to 460 nm.

The reaction time is 12-36 h.

The reaction temperature is 10-40 ℃.

The post-processing comprises: diluting with water and ethyl acetate, extracting the water phase twice with ethyl acetate, mixing the extracted organic phases, washing with saturated sodium chloride, drying with anhydrous magnesium sulfate, and separating.

The substitution includes substitution with an alkyl group, an alkoxy group, a carboxyalkyl group, an alkanoyl group, a keto group, an alkylamino group, a halogen atom or a nitro group. In some embodiments, the substitution comprises substitution with methyl, ethyl, propyl, tert-butyl, methoxy, carboxymethyl, acetyl, keto, methylamino, chlorine, or nitro.

The heteroatom of the heterocyclic or heteroaromatic ring may be a nitrogen atom, an oxygen atom or a sulfur atom.

In some embodiments, the R is₁Including groups selected from methyl, phenyl, 4-tolyl, 4-methoxyphenyl, 2-pyridyl, 6-methyl-2-pyridyl, 3, 5-dimethylphenyl, indanyl, 3, 4-dihydro-2H-chromenyl, thiopyranyl, or the following c, d, e, f structures:

in some embodiments, the R is₂IncludedSelected from the group consisting of methyl, phenyl, 4-tolyl, 2-pyridyl, propyl, 6-methyl-2-pyridyl, 2-furyl, 5-methyl-2-thienyl, 3, 5-dimethylphenyl, 4-tert-butylphenyl and 4-nitrophenyl.

In some embodiments, the R is₃Including a group selected from a hydrogen atom, phenyl group, methyl group, 2-naphthyl group, 4-chlorophenyl group, N-methyl-2-pyrrolyl group, 4-pyridyl group, 3-thienyl group, 2-thienyl group, 4-methylphenyl group, 4-tert-butylphenyl group, 4-phenylphenyl group and 2-furyl group.

In some embodiments, the R is₄Including a hydrogen atom, phenyl group, ester group, methyl group, 4-methoxyphenyl group, carbonyl group, and cyano group.

In some embodiments, the R is₁、R₄Together with the atoms to which they are attached form a substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted cycloheptenyl, phenyl, 4-tolyl, 4-methoxyphenyl, substituted or unsubstituted pyridyl, 3, 5-dimethylphenyl, 1H-indenyl, 1, 2-dihydronaphthyl, 2H-chromenyl, thiopyranyl.

In some embodiments, the R is₁、R₄Together with the atoms to which they are attached, form the following structure:

In some embodiments, the compound of formula II comprises a structure selected from:

in a second aspect, the invention provides the use of a photosensitizer and a cobalt oxime complex in the preparation of a pyridine compound.

Use of a photosensitizer comprising at least one member selected from the group consisting of the structures of the photosensitizer of the first aspect and a cobalt oxime complex in the preparation of a pyridine-based compound; the cobalt oxime complex comprises at least one selected from the structures of the cobalt oxime complex of the first aspect.

Advantageous effects

Compared with the prior art, the invention has the following technical effects:

(1) based on the development concept of sustainable chemistry, the invention adopts the photosensitizer and the cobalt oxime compound as the catalyst to prepare the pyridine compound, and has the advantages of safety, mildness, high efficiency and economy. Meanwhile, the cobalt oxime compound catalyst is insensitive to water and oxygen, has low requirement on reaction and can greatly reduce the operation difficulty.

Definition of terms

Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:

in the present invention, the expression "compound I" and "compound represented by formula I" means the same compound.

"ambient temperature" in the present invention refers to ambient temperature, and the temperature is from about 10 ℃ to about 40 ℃. In some embodiments, "room temperature" refers to a temperature of from about 20 ℃ to about 30 ℃; in other embodiments, "room temperature" refers to a temperature of from about 25 ℃ to about 30 ℃; in still other embodiments, "room temperature" refers to 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, etc.

In the present invention, "trace" means a yield of less than 3%.

In the present invention, the dotted line "- - -" in the chemical formula indicates a noncovalent bond such as a hydrogen bond, van der waals force, or the like.

An "alkyl" group is a hydrocarbon containing an n-carbon atom, a secondary carbon atom, a tertiary carbon atom, or a ring carbon atom. For example, the alkyl group can have 1 to 10 carbon atoms (i.e., C)₁-C₁₀Alkyl), 1 to 8 carbon atoms (i.e., C)₁-C₈Alkyl) or 1 to 6 carbon atoms (i.e., C)₁-C₆Alkyl groups). Examples of suitable alkyl groups include, but are not limited to, methyl (Me, -CH)₃) Ethyl (Et-CH)₂CH₃) 1-propyl (i-Pr, i-propyl, -CH)₂CH₂CH₃) 2-propyl (i-Pr, i-propyl, -CH (CH)₃)₂) 1-butyl (n-Bu, n-butyl, -CH)₂CH₂CH₂CH₃) 2-methyl-1-propyl (i-Bu, i-butyl, -CH)₂CH(CH₃)₂) 2-butyl (s-Bu, s-butyl, -CH (CH)₃)CH₂CH₃) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH)₃)₃) 1-pentyl (n-pentyl, -CH)₂CH₂CH₂CH₂CH₃) 2-pentyl (-CH (CH)₃)CH₂CH₂CH₃) 3-pentyl (-CH (CH)₂CH₃)₂) 2-methyl-2-butyl (-C (CH)₃)₂CH₂CH₃) 3-methyl-2-Butyl (-CH (CH)₃)CH(CH₃)₂) 3-methyl-1-butyl (-CH)₂CH₂CH(CH₃)₂) 2-methyl-1-butyl (-CH)₂CH(CH₃)CH₂CH₃) 1-hexyl (-CH)₂CH₂CH₂CH₂CH₂CH₃) 2-hexyl (-CH (CH)₃)CH₂CH₂CH₂CH₃) 3-hexyl (-CH (CH)₂CH₃)(CH₂CH₂CH₃) 2-methyl-2-pentyl (-C (CH))₃)₂CH₂CH₂CH₃) 3-methyl-2-pentyl (-CH (CH)₃)CH(CH₃)CH₂CH₃) 4-methyl-2-pentyl (-CH (CH)₃)CH₂CH(CH₃)₂) 3-methyl-3-pentyl (-C (CH)₃)(CH₂CH₃)₂) 2-methyl-3-pentyl (-CH (CH)₂CH₃)CH(CH₃)₂)2, 3-dimethyl-2-butyl (-C (CH)₃)₂CH(CH₃)₂) 3, 3-dimethyl-2-butyl (-CH (CH)₃)C(CH₃)₃And octyl (- (CH)₂)₇CH₃)。

"alkenyl" is intended to include groups having at least one site of unsaturation, i.e., carbon-carbon sp²A hydrocarbon of a positive carbon atom, a secondary carbon atom, a tertiary carbon atom or a ring carbon atom of a double bond. For example, the alkenyl group may have 2 to 10 carbon atoms (C)₂-C₁₀Alkenyl), 2 to 12 carbon atoms (C)₂-C₁₂Alkenyl) or 2 to 6 carbon atoms (C)₂-C₆Alkenyl). Examples of suitable alkenyl groups include, but are not limited to, ethylene or vinyl (-CH ═ CH)₂) Allyl (-CH)₂CH＝CH₂) Cyclopentenyl (-C)₅H₇) And 5-hexenyl (-CH)₂CH₂CH₂CH₂CH＝CH₂)。

"aryl" means an aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system. For example, the aryl group can have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. Typical aryl groups include, but are not limited to, groups derived from benzene (e.g., phenyl), substituted benzenes, naphthalenes, anthracenes, biphenyls, and the like.

The term "substituted" as used in reference to alkyl, aryl, heterocyclyl, heteroaryl, carbocyclyl, and the like is substituted C₁-C₁₀Alkyl group "," substituted C₆-C₂₀Aryl group and substituted C₁-C₂₀Heterocycle "and" substituted carbocyclyl "each mean C wherein one or more hydrogen atoms are each independently replaced with a non-hydrogen substituent₁-C₁₀Alkyl radical, C₆-C₂₀Aryl, arylalkyl, C₁-C₂₀Heterocycle, carbocyclyl. Unless otherwise indicated, when the term "substituted" is used in conjunction with a group having two or more moieties capable of substitution, such as arylalkyl, the substituent may be attached to the aryl moiety, the alkyl moiety, or both.

As used herein, "heterocycle" or "heterocyclyl" includes by way of example and not limitation those heterocycles described in: paquette, Leo a.: principles of Modern Heterocyclic Chemistry (w.a. benjamin, New York, 1968), in particular chapters 1, 3, 4, 6, 7 and 9: the Chemistry of Heterocyclic Compounds, A Series of monograms ^ (John Wiley & Sons, New York, 1950 to now), especially volumes 13, 14, 16, 19 and 28 and J.Am.chem.Soc. (1960) 82: 5566. in a particular embodiment of the invention, "heterocycle" includes "carbocycle" as defined herein, wherein one or more (e.g. 1, 2, 3 or 4) carbon atoms have been replaced by a heteroatom (e.g. O, N or S). The term "heterocycle" or "heterocyclyl" includes saturated rings, partially unsaturated rings, and aromatic rings (i.e., heteroaromatic rings). Substituted heterocyclyl groups include, for example, heterocyclic groups substituted with any of the substituents disclosed herein including carbonyl.

Examples of heterocycles include, by way of example and not by way of limitation, pyridyl, dihydropyridinyl, tetrahydropyridinyl (piperidinyl), thiazolyl, tetrahydrothienyl, thiooxidised tetrahydrothienyl, pyrimidinyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, tetrazolyl, benzofuryl, thianaphthyl, indolyl, indolinyl, quinolinyl, isoquinolinyl, benzimidazolyl, piperidinyl, 4-piperidonyl, pyrrolidinyl, 2-pyrrolidinonyl, pyrrolinyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, octahydroisoquinolinyl, azocin (azocane), triazinyl, 6H-1, 2, 5-thiadiazinyl, 2H, 6H-1, 5, 2-dithiazinyl, thienyl, thianthrenyl, pyranyl, isobenzofuryl, indolinyl, quinolyl, and the like, Chromenyl, xanthenyl, phenoflavinyl, 2H-pyrrolyl, isothiazolyl, isoxazolyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, IH-indazolyl, purinyl, 4H-quinolizinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4 aH-carbazolyl, beta-carbolinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, oxazolidinyl, benzotriazolyl, benzisoxazolyl, oxindolyl, benzoxazolinyl, indigosoyl, and bis-tetrahydrofuranyl.

"heteroaryl" refers to an aromatic heterocyclic group having at least one heteroatom in the ring. Non-limiting examples of suitable heteroatoms that may be included on the aromatic ring include oxygen, sulfur, and nitrogen. Non-limiting examples of heteroaryl rings include all those aromatic rings listed in the definition of "heterocyclyl" including pyridyl, pyrrolyl, oxazolyl, indolyl, isoindolyl, purinyl, furyl, thienyl, benzofuryl, benzothienyl, carbazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrimidinyl, pyrazolyl and the like.

Whenever a compound described herein is substituted with more than one of the same named group (e.g., "R" or "R")¹") it is to be understood that these groups may be the same or different, i.e., each group is independently selected.

In the present invention, the names of the reagents are shown in the following table.

For short	Name of Chinese
		DCM	Methylene dichloride
THF	Tetrahydrofuran (THF)
		Dioxane	Dioxane (dioxane)
DCE	Dichloroethane
		Toulene	Toluene
MeCN	Acetonitrile
		DABCO	Triethylene diamine
TFA	Trifluoroacetic acid
		sc(OTf)₃	Scandium triflate
TsOH	P-toluenesulfonic acid
		MsOH	Methanesulfonic acid
Y(OTf)₃	Yttrium trifluoromethanesulfonate (UTS)
		AcOH	Acetic acid

Detailed Description

In order to make the technical solutions of the present invention better understood by those skilled in the art, some non-limiting examples are further disclosed below to further explain the present invention in detail.

The reagents used in the present invention are either commercially available or can be prepared by the methods described herein.

Example 1: screening of photosensitizers

To a 10mL Schlenk tube were added 25.2mg of Compound a (0.1mmol, 1eq) and 15.4mg of Compound b (0.2mmol, 2eq), 2.3ul CH₃COOH (0.02mmol) and 16.8mg of triethylenediamine (0.15mmol, 1.5eq) were added, according to Table 1, 0.002mmol of the corresponding photosensitizer and 0.004mmol of the cobalt oxime complex Co (dmgH)₂Cl (DMAP), vacuumizing, replacing with nitrogen for 3 times, adding 1.0mL of anhydrous acetonitrile under the protection of nitrogen flow, irradiating for 24 hours at 25 ℃ by using a 30W blue LED lamp (the wavelength is 420-475 nm), after the reaction is finished, extracting the reaction liquid by using 5mL of water and 10mL of ethyl acetate, extracting the water phase by using ethyl acetate (5mL multiplied by 2), combining the extracted organic phases, washing the combined organic phases by using saturated saline solution, drying by using anhydrous magnesium sulfate, and carrying out column chromatography (the eluent is a petroleum ether and ethyl acetate system) to separateSeparation and purification to obtain compound 2 (white solid); the yields of compound 2 obtained are shown in table 1.

Table 1: screening results for photosensitizers

Taking the obtained compound 2 to detect the hydrogen spectrum and the mass spectrum, and obtaining the result:

hydrogen spectrum:¹H NMR(400MHz，Chloroform-d)δ8.20(dd，J＝7.3，1.9Hz，4H)，7.82(dd，J＝8.5，7.1Hz，1H)，7.71(d，J＝7.8Hz，2H)，7.53(dd，J＝8.4，6.6Hz，4H)，7.50-7.40(m，2H)；¹³C NMR(101MHz，Chloroform-d)δ156.87，139.55，137.53，129.03，128.74，127.05，118.68。

mass spectrum: HR-MS (ESI) calcd for C₁₇H₁₄N⁺[M+H]⁺232.1121 found 232.1119。

Example 2: screening of cobalt oxime complexes

The procedure of example 1 was followed except that the photosensitizer and the cobalt oxime complex were replaced with the photosensitizer and the cobalt oxime complex shown in Table 2, and the photosensitizer and the cobalt oxime complex were fed in the same molar amounts as those of the photosensitizer and the cobalt oxime complex of example 1, respectively, and the procedure of example 1 was otherwise followed; compound 2 was prepared and the yields of compound 2 obtained are shown in table 2.

Table 2: screening results of cobalt oxime complexes

The hydrogen spectrum and the mass spectrum of the obtained compound 2 were measured, and the results were the same as those of example 1.

Example 3: screening of Ammonia sources

The same procedures as in example 1 were carried out except that the method described in example 1 was followed, and the compound b, the photosensitizer and the cobalt oxime complex were replaced with the ammonia source, the photosensitizer and the cobalt oxime complex shown in Table 3, and the molar amounts of the ammonia source, the photosensitizer and the cobalt oxime complex fed were the same as those of the compound b, the photosensitizer and the cobalt oxime complex in example 1, respectively; compound 2 was prepared and the yields of compound 2 obtained are shown in table 3.

Table 3: results of screening for Ammonia sources

Example 4: screening of solvents

The procedure of example 1 was followed while replacing anhydrous acetonitrile, a photosensitizer and a cobalt oxime complex with the solvent, the photosensitizer and the cobalt oxime complex shown in Table 4, the volume of the solvent added was the same as that of the anhydrous acetonitrile of example 1, the molar amounts of the photosensitizer and the cobalt oxime complex added were the same as those of the photosensitizer and the cobalt oxime complex of example 1, respectively, and the rest was the same as that of example 1; compound 2 was prepared and the yields of compound 2 obtained are shown in table 4.

Table 4: screening results of solvent

Example 5: screening for bases

The procedure of example 1 was followed except that triethylenediamine, the photosensitizer and the cobalt oxime complex were replaced with the bases, the photosensitizers and the cobalt oxime complexes shown in Table 5, and the molar amounts of the bases, the photosensitizers and the cobalt oxime complexes fed were the same as those of the bases, the photosensitizers and the cobalt oxime complexes of example 1, respectively; compound 2 was prepared and the yields of compound 2 obtained are shown in table 5.

Table 5: screening results for bases

Numbering	Photosensitizers	Cobalt oxime complexes	Alkali	Conversion of Compound a	Yield of
						1	Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	K₂CO₃	17％	Trace
2	Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	Cs₂CO₃	5％	Trace
						3	Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	NaOAc	48％	28％
4	Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	KOAc	12％	Trace
						5	[Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	Et₃N	48％	Trace
6	[Ir(ppy)₂(bpy)]PF₆	Co(dmgBF₂)₂.2H₂O	DABCO	90％	64％

Example 6: screening for acids

The procedure of example 1 was followed except that scandium trifluoromethanesulfonate, the photosensitizer and the cobalt oxime complex were replaced with the acid, the photosensitizer and the cobalt oxime complex shown in Table 6, the acid, the photosensitizer and the cobalt oxime complex were fed in the same molar amounts as those of the acid, the photosensitizer and the cobalt oxime complex of example 1, respectively, and the procedure of example 1 was followed; compound 2 was prepared and the yields of compound 2 obtained are shown in table 6.

Table 6: screening results for acids

Example 7: condition control test

Taking 25.2mg of compound a (0.1mmol, 1eq) and compound b (0.2mmol, 2eq), the dosage of compound b is shown in Table 7, respectively adding the acid and the base which are shown in Table 7, and the dosage molar quantity of the acid and the base is shown in example 1; adding a photosensitizer and a cobalt oxime compound according to the following table 7, vacuumizing and replacing 3 times with nitrogen, adding 1.0mL of anhydrous acetonitrile under the protection of nitrogen flow, irradiating for 24 hours (no irradiation in group 3) by using a 30W blue LED lamp (with the wavelength of 420-475 nm) at 25 ℃, extracting a reaction solution by using 5mL of water and 10mL of ethyl acetate after the reaction is finished, extracting a water phase by using ethyl acetate (5mL multiplied by 2), combining extracted organic phases, washing the combined organic phases by using saturated saline solution, drying by using anhydrous magnesium sulfate, and separating and purifying by column chromatography (an eluent is a petroleum ether/ethyl acetate system) to obtain a compound 2 (white solid); the yields of compound 2 obtained are shown in table 8.

Table 7: conditions of variables of condition control test

Table 8: results of Condition control test

Numbering	Conversion of Compound a	Yield of
			1	58％	trace
2	74％	28％
			3	33％	trace
4	63％	22％
			5	44％	19％
6	100％	42％
			7	81％	65％
8	59％	43％

Example 8: preparation of Compound 1

To a 10ml Schlenk tube were added 12.8mg of Compound 67(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 63% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 5.9mg of Compound 1 (pale yellow oily liquid, 55% yield). The obtained compound 1 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ7.45(t，J＝7.6Hz，1H)，6.94(d，J＝7.6Hz，2H)，2.51(s，6H)。

¹³C NMR(151MHz，Chloreform-d)δ157.65，136.56，120.18，24.44。

HR-MS(ESI)calcd for C₇H₁₀N⁺[M+H]⁺108.0808 found 108.0811。

example 9: preparation of Compound 3

To a 10ml Schlenk tube was added 19.0mg of Compound 68(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4 mg)，0.2mmol，2equiv.)，Co(dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is 88 percent determined by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 14.4mg of Compound 3 (pale yellow oily liquid, 85% yield). The obtained compound 3 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.01-7.95(m，2H)，7.63(t，J＝7.7Hz，1H)，7.51(d，J＝7.8Hz，1H)，7.50-7.43(m，2H)，7.43-7.36(m，1H)，7.10(d，J＝7.6Hz，1H)，2.63(s，3H)。

¹³C NMR(101MHz，Chloroform-d)δ158.39，157.02，139.82，136.89，128.71，128.69，127.02，121.61，117.65，24.78。

HR-MS(ESI)calcd for C₁₂H₁₂N⁺[M+H]⁺170.0964 found 170.0963。

example 10: preparation of Compound 66

To a 10ml Schlenk tube were added 24.4mg of Compound 69(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. Placing the reaction tube in a 30W blue light lamp for irradiating for 24 hours, and after the reaction is finishedThe Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 94% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 19.8mg of compound 66 (pale yellow oily liquid, 89% yield). The obtained compound 66 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ7.44-7.40(m，2H)，7.39-7.35(m，1H)，7.29-7.26(m，2H)，6.84(s，1H)，2.97(t，J＝6.6Hz，2H)，2.58(t，J＝6.4Hz，2H)，2.51(s，3H)，1.95-1.86(m，2H)，1.71(qd，J＝9.0，7.6，4.5Hz，2H)。

¹³C NMR(151MHz，Chloroform-d)δ156.81，154.68，150.02，139.63，128.50，128.24，127.63，126.74，121.57，33.01，27.09，24.01，23.09，23.06。

HR-MS(ESI)calcd for C₁₆H₁₈N⁺[M+H]⁺224.1434 found 224.1441。

example 11: preparation of Compound 6

To a 10ml Schlenk tube were added 23.0mg of Compound 70(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then the organic phase was combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentratedConcentrating the organic phase, adding dibromomethane as an internal nuclear magnetic standard, and determining the reaction yield to be 85% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 16.3mg of Compound 6 (pale yellow oily liquid, 78% yield). The obtained compound 6 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ7.99-7.89(m，2H)，7.47-7.39(m，4H)，7.39-7.34(m，1H)，3.00(t，J＝6.4Hz，2H)，2.80(t，J＝6.3Hz，2H)，1.93(tdd，J＝8.4，5.3，2.6Hz，2H)，1.85(dtt，J＝9.4，6.1，2.8Hz，2H)。

¹³C NMR(101MHz，Chloroform-d)δ157.27，154.71，139.95，137.45，130.75，128.64，128.36，126.85，117.95，32.86，28.58，23.23，22.82。

HR-MS(ESI)calcd for C₁₅H₁₆N⁺[M+H]⁺210.1275 found 210.1277。

example 12: preparation of Compound 4

To a 10ml Schlenk tube were added 32.8mg of Compound 71(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 81% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 23.0mg of Compound 4 (pale yellow oily liquid, 75% yield). Taking the obtained compound 6 to perform hydrogen spectrum,And (3) detecting by carbon spectrum and mass spectrum, and obtaining the following results:

¹H NMR(400MHz，Chloroform-d)δ8.27-8.17(m，4H)，7.90(s，2H)，7.81-7.71(m，2H)，7.58-7.50(m，6H)，7.50-7.42(m，3H。

¹³C NMR(101MHz，Chloroform-d)δ157.54，150.23，139.62，139.10，129.14，129.07，129.00，128.73，127.22，127.16，117.16。

HR-MS(ESI)calcd for C₂₃H₁₈N⁺[M+H]⁺308.1434 found 308.1431。

example 13: preparation of Compound 5

To a 10ml Schlenk tube were added 18.2mg of Compound 72(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 93% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 14.0mg of Compound 5 (pale yellow oily liquid, 87% yield). The obtained compound 5 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ6.77(s，1H)，2.87(t，J＝6.0Hz，2H)，2.59(t，J＝6.1Hz，2H)，2.44(s，3H)，2.16(s，3H)，1.83(tdd，J＝11.3，6.4，2.6Hz，4H)。

¹³C NMR(151MHz，Chloroform-d)δ155.79，154.28，146.16，127.95，122.21，32.88，25.48，23.80，22.97，22.91，18.82。

HR-MS(ESI)calcd for C₁₁H₁₆N⁺[M+H]⁺162.1277 found 162.1276。

example 14: preparation of Compound 7

To a 10ml Schlenk tube were added 34.2mg of Compound 73(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had separated, the aqueous phase was extracted twice with ethyl acetate (5 m.times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 87% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 27.3mg of compound 7 (white solid, 85% yield). The obtained compound 7 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ7.21-7.15(m，2H)，7.13(s，1H)，7.09(ddd，J＝9.1，4.3，2.0Hz，6H)，7.01-6.91(m，5H)，6.80-6.75(m，2H)，2.61(s，3H)。

¹³C NMR(101MHz，Chloroform-d)δ157.90，156.92，150.01，141.01，139.68，137.93，131.61，131.52，129.91，129.31，127.86，127.63，127.61，127.25，127.20，126.40，123.26，24.47。

HR-MS(ESI)calcd for C₂₄H₂₀N⁺[M+H]⁺322.1590 found 322.1586。

example 15: preparation of Compound 8

To a 10ml Schlenk tube was added 35.6mg of Compound 74(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 53% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 17.1mg of Compound 8 (pale yellow oily liquid, 51% yield). The obtained compound 8 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.49(dd，J＝7.8，1.7Hz，1H)，8.20-8.12(m，2H)，7.63(s，1H)，7.51(tdd，J＝10.0，6.3，3.3Hz，5H)，7.48-7.41(m，1H)，7.35(ddd，J＝13.0，7.7，1.7Hz，3H)，7.16(td，J＝7.5，1.1Hz，1H)，6.98(dd，J＝8.2，1.1Hz，1H)，5.27(s，2H)。

¹³C NMR(101MHz，Chloroform-d)δ156.47，156.20，148.78，147.34，139.16，137.58，131.22，129.12，128.80，128.74，128.63，128.48，126.96，125.38，123.83，122.33，122.17，119.99，116.78，65.96。

HR-MS(ESI)calcd for C₂₄H₁₈NO⁺[M+H]⁺336.1383 found 336.1379。

example 16: preparation of Compound 9

To a 10ml Schlenk tube was added 35.4mg of Compound 75(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 58% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 18.3mg of compound 9 (pale yellow solid, 55% yield). The obtained compound 9 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.59(dd，J＝7.8，1.4Hz，1H)，8.22-8.16(m，2H)，7.61(s，1H)，7.55-7.45(m，5H)，7.45-7.40(m，4H)，7.34(td，J＝7.4，1.5Hz，1H)，7.25-7.21(m，1H)，2.99-2.92(m，2H)，2.87(dd，J＝9.3，6.0Hz，2H)。

¹³C NMR(101MHz，Chloroform-d)δ154.44，152.60，149.27，139.57，139.36，138.19，135.23，129.06，128.83，128.72，128.66，128.48，128.02，127.93，127.48，127.08，126.82，125.75，119.95，28.18，25.30。

HR-MS(ESI)calcd for C₂₅H₂₀N⁺[M+H]⁺334.1590 found 334.1586。

example 17: preparation of Compound 10

To a 10ml Schlenk tube were added 34.0mg of Compound 76(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 65% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 18.8mg of compound 10 (white solid, 59% yield). The obtained compound 10 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.27(d，J＝7.4Hz，1H)，8.23-8.13(m，2H)，7.69(s，1H)，7.69-7.65(m，2H)，7.60-7.39(m，9H)，4.03(s，2H)。

¹³C NMR(101MHz，Chloroform-d)δ161.18，157.20，146.43，144.13，141.21，139.92，138.93，132.90，128.89，128.77，128.75，128.72，128.57，128.26，127.24，127.20，124.98，121.43，118.24，34.44。

HR-MS(ESI)calcd for C₂₄H₁₈N⁺[M+H]⁺320.1434 found 320.1431。

example 18: preparation of Compound 11

To a 10ml Schlenk tube were added 40.4mg of Compound 77(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol) DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol) were evacuated and replaced 3 times with nitrogen and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 51% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 18.0mg of compound 11 (white solid, 47% yield). The obtained compound 11 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.23-8.13(m，2H)，7.78(s，1H)，7.49(dd，J＝8.3，6.5Hz，2H)，7.46-7.41(m，1H)，7.41-7.35(m，2H)，7.22(ddd，J＝10.5，5.0，2.0Hz，6H)，7.17-7.11(m，2H)，7.10-7.03(m，3H)，6.95-6.89(m，2H)。

¹³C NMR(101MHz，Chloroform-d)δ156.92，154.55，149.66，139.88，138.80，138.00，136.81，131.87，130.40，129.17，128.30，127.99，127.67，126.90，126.68，126.48，126.36，126.32，126.05，125.56，119.36。

HR-MS(ESI)calcd for C₂₉H₂₂N⁺[M+H]⁺384.1747 found 384.1742。

example 19: preparation of Compound 12

To a 10ml Schlenk tube were added 32.4mg of Compound 78(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and added under the protection of a stream of nitrogen1.0mL of anhydrous acetonitrile was added. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 92% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 26.7mg of compound 12 (white solid, 88% yield). The obtained compound 12 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.04-7.86(m，2H)，7.50(s，1H)，7.42-7.30(m，8H)，3.57(s，3H)，2.63(s，3H)。

¹³C NMR(151MHz，Chloroform-d)δ168.53，156.49，154.79，147.88，137.79，137.72，128.36，127.77，127.64，127.57，126.76，126.19，125.48，117.51，51.19，22.18。

HR-MS(ESI)calcd for C₂₀H₁₈NO₂ ⁺[M+H]⁺304.1332 found 304.1329。

example 20: preparation of Compound 13

To a 10ml Schlenk tube were added 35.6mg of Compound 79(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then the organic phase was combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentratedAnd concentrating the organic phase, adding dibromomethane as a nuclear magnetic internal standard, and determining the reaction yield to be 63% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 17.1mg of compound 13 (white solid, 51% yield). The obtained compound 13 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.11-8.06(m，2H)，7.60(d，J＝3.7Hz，2H)，7.57(d，J＝1.4Hz，1H)，7.52-7.35(m，8H)，7.30(d，J＝7.8Hz，2H)，2.44(s，3H)，2.27(s，3H)。

¹³C NMR(101MHz，Chloroform-d)δ159.45，153.96，151.61，140.39，139.36，138.54，137.70，129.40，128.82，128.79，128.62，128.47，127.88，126.95，126.92，119.83，21.36，18.08。

HR-MS(ESI)calcd for C₂₅H₂₂N⁺[M+H]⁺336.1747 found 336.1744。

example 21: preparation of Compound 14

To a 10ml Schlenk tube were added 37.8mg of Compound 80(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 77% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 25.3mg of compound 14 (white solid, 71% yield). Taking the obtained compound 14 for hydrogen spectrum, carbon spectrum and mass spectrum detectionThe results were as follows:

¹H NMR(600MHz，Chloroform-d)δ8.17-8.13(m，4H)，8.11(s，1H)，7.91(s，2H)，7.90(d，J＝8.4Hz，1H)，7.88-7.85(m，1H)，7.84-7.79(m，1H)，7.75(dd，J＝8.5，1.6Hz，1H)，7.49-7.42(m，6H)，7.40-7.35(m，2H)。

¹³C NMR(151MHz，Chloroform-d)δ157.63，150.14，139.65，136.34，133.57，133.48，129.12，128.98，128.77，128.49，127.81，127.22，126.81，126.75，126.52，124.88，117.35。

HR-MS(ESI)calcd for C₂₇H₂₀N⁺[M+H]⁺358.1590 found 358.1586。

example 22: preparation of Compound 15

To a 10ml Schlenk tube were added 42.2mg of Compound 81(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 44% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 16.4mg of compound 15 (white solid, 41% yield). The obtained compound 15 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.20-8.11(m，4H)，7.71(s，2H)，7.70-7.60(m，2H)，7.53-7.46(m，2H)，7.10-6.98(m，4H)，3.89(s，6H)。

¹³C NMR(101MHz，Chloroform-d)δ160.60，157.12，148.78，137.77，135.03，132.11，129.28，128.46，128.40，115.41，114.08，55.41。

HR-MS(ESI)calcd for C₂₅H₂₁ClNO₂ ⁺[M+H]⁺402.1255 found 402.1252。

example 23: preparation of Compound 16

To a 10ml Schlenk tube were added 33.1mg of Compound 82(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 64% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 18.6mg of compound 16 (white solid, 60% yield). The obtained compound 16 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.25-8.10(m，4H)，7.72(s，2H)，7.52(dd，J＝8.2，6.5Hz，4H)，7.50-7.39(m，2H)，6.84(t，J＝2.3Hz，1H)，6.53(dd，J＝3.7，1.8Hz，1H)，6.29(dd，J＝3.7，2.7Hz，1H)，3.84(s，3H)。

¹³C NMR(101MHz，Chloroform-d)δ157.20，142.16，139.57，132.38，129.08，128.75，127.11，125.90，117.67，110.70，108.59，35.65。

HR-MS(ESI)calcd for C₂₂H₁₉N₂ ⁺[M+H]⁺311.1543 found 311.1540。

example 24: preparation of Compound 17

To a 10ml Schlenk tube were added 37.2mg of Compound 83(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 78% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 25.6mg of compound 17 (white solid, 73% yield). The obtained compound 17 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(600MHz，Chloroform-d)δ8.10-8.04(m，2H)，7.61(s，1H)，7.49(t，J＝7.5Hz，2H)，7.45-7.39(m，1H)，7.22(dd，J＝5.4，1.8Hz，3H)，7.13(dd，J＝6.6，2.9Hz，2H)，7.01(d，J＝8.4Hz，2H)，6.81(d，J＝8.5Hz，2H)，3.79(s，3H)，2.52(s，3H)。

¹³C NMR(151MHz，Chloroform-d)δ157.41，156.32，154.31，148.76，138.85，138.40，132.38，130.35，129.48，128.25，127.73，127.69，126.87，126.20，125.96，118.33，112.52，54.12，23.32。

HR-MS(ESI)calcd for C₂₅H₂₂NO⁺[M+H]⁺352.1696 found 352.1693。

example 25: preparation of Compound 18

To a 10ml Schlenk tube were added 32.9mg of Compound 84(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 73 percent by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 23.1mg of compound 18 (white solid, 75% yield). The obtained compound 18 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.86(s，2H)，8.20(dd，J＝7.9，4.0Hz，4H)，7.89(d，J＝4.0Hz，2H)，7.70(s，2H)，7.53(dt，J＝11.0，5.1Hz，4H)，7.47(q，J＝7.3，6.2Hz，2H)。

¹³C NMR(151MHz，Chloroform-d)δ158.07，150.32，147.28，146.96，139.05，129.45，128.85，127.16，122.10，116.67。

HR-MS(ESI)calcd for C₂₂H₁₇N₂ ⁺[M+H]⁺309.1386 found 309.1383。

example 26: preparation of Compound 19

To a 10ml Schlenk tube were added 33.0mg of Compound 85(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 73 percent by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 21.6mg of compound 19 (white solid, 70% yield). The obtained compound 19 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.75(s，2H)，8.73(ddd，J＝4.8，1.8，0.9Hz，2H)，8.67(dt，J＝7.9，1.1Hz，2H)，7.94-7.82(m，4H)，7.51(dd，J＝8.3，6.5Hz，2H)，7.48-7.43(m，1H)，7.35(ddd，J＝7.5，4.8，1.2Hz，2H)。

¹³C NMR(101MHz，Chloroform-d)δ156.23，155.89，150.38，149.12，138.48，136.95，129.05，128.95，127.37，123.87，121.42，118.98。

HR-MS(ESI)calcd for C₂₁H₁₆N₃ ⁺[M+H]⁺310.1339 found 310.1337。

example 27: preparation of Compound 20

To a 10ml Schlenk tube were added 33.4mg of Compound 86(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under protection of a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 78% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 23.5mg of compound 20 (white solid, 75% yield). The obtained compound 20 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(400MHz，Chloroform-d)δ8.24-8.18(m，4H)，7.88(s，2H)，7.77(dd，J＝3.0，1.4Hz，1H)，7.58-7.54(m，2H)，7.53-7.49(m，4H)，7.49-7.43(m，2H)。

¹³C NMR(101MHz，Chloroform-d)δ157.67，144.48，140.29，139.54，129.10，128.73，127.14，127.08，126.04，123.03，116.32。

HR-MS(ESI)calcd for C₂₁H₁₆NS⁺[M+H]⁺314.0998 found 314.0996。

example 28: preparation of Compound 22

To a 10ml Schlenk tube were added 32.5mg of Compound 87(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. Layering of the liquid to be treatedAfter that, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 87% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 25.2mg of compound 22 (white solid, 83% yield). The obtained compound 22 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.67(ddd，J＝4.8，1.8，0.9Hz，1H)，8.49(dt，J＝7.9，1.1Hz，1H)，8.30(s，1H)，7.83(td，J＝7.7，1.8Hz，1H)，7.47-7.42(m，4H)，7.41-7.38(m，1H)，7.32(ddd，J＝7.5，4.7，1.2Hz，1H)，3.66(s，3H)，2.71(s，3H)。

¹³C NMR(151MHz，Chloroform-d)δ169.61，155.90，155.49，155.42，149.21，149.09，138.71，137.02，128.58，128.57，127.93，127.90，124.07，121.66，119.04，52.26，23.16。

HR-MS(ESI)calcd for C₁₉H₁₇N₂O₂ ⁺[M+H]⁺302.1285 found 305.1282。

example 29: preparation of Compound 25

To a 10ml Schlenk tube were added 35.7mg of Compound 88(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then the organic phase was combined and washed with saturated brine, dried over anhydrous magnesium sulfate,concentrating the organic phase, adding dibromomethane as an internal nuclear magnetic standard, and determining the reaction yield to be 69% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 22.8mg of compound 25 (pale yellow oily liquid, 68% yield). The obtained compound 25 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(600MHz，Chloroform-d)δ8.70-8.65(m，2H)，8.48(dd，J＝7.7，1.7Hz，1H)，8.36(s，1H)，7.87(td，J＝7.7，1.9Hz，1H)，7.52-7.44(m，3H)，7.41-7.38(m，2H)，7.38-7.32(m，2H)，7.17(td，J＝7.5，1.1Hz，1H)，6.99(dd，J＝8.1，1.1Hz，1H)，5.29(s，2H)。

¹³C NMR(151MHz，Chloroform-d)δ156.48，156.04，154.88，149.03，148.48，147.65，137.41，136.99，131.26，128.68，128.59，125.21，123.86，123.83，123.73，122.33，121.38，120.67，116.87，66.08。

HR-MS(ESI)calcd for C₂₃H₁₇N₂O⁺[M+H]⁺337.1335 found 337.1331。

example 30: preparation of Compound 26

To a 10ml Schlenk tube was added 40.5mg of Compound 89(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then the organic phase is combined and washed by saturated saline solution, after anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 42 through nuclear magnetic hydrogen spectrum% of the total weight of the composition. Purification by column chromatography gave 14.2mg of compound 26 (white solid, 37% yield). The obtained compound 26 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.70(d，J＝4.8Hz，1H)，8.62(d，J＝8.0Hz，1H)，8.48(s，1H)，7.84(td，J＝7.7，1.8Hz，1H)，7.39(dd，J＝6.8，2.8Hz，2H)，7.33(dd，J＝7.4，4.9Hz，1H)，7.25-7.19(m，6H)，7.16(p，J＝3.6Hz，2H)，7.08(tt，J＝8.6，4.6Hz，3H)，6.97-6.92(m，2H)。

¹³C NMR(151MHz，Chloroform-d)δ157.69，156.04，154.27，150.94，149.00，140.93，139.64，137.90，137.00，134.45，131.40，130.18，129.47，127.82，127.74，127.56，127.43，127.29，126.68，123.77，121.60，121.01。

HR-MS(ESI)calcd for C₂₈H₂₁N₂ ⁺[M+H]⁺385.1699 found 385.1696。

example 31: preparation of Compound 27

To a 10ml Schlenk tube were added 34.1mg of Compound 90(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 75% by nuclear magnetic hydrogen spectrum. Column chromatography separation and purification gave 22.7mg of Compound 27 (white)Solid, yield 71%). The obtained compound 27 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(600MHz，Chloroform-d)δ8.75-8.65(m，2H)，8.44(d，J＝1.7Hz，1H)，8.26(d，J＝7.5Hz，1H)，7.93-7.84(m，1H)，7.72(dd，J＝7.2，1.8Hz，2H)，7.56(d，J＝7.4Hz，1H)，7.55-7.50(m，2H)，7.50-7.40(m，3H)，7.32(dd，J＝7.1，4.7Hz，1H)，4.02(s，2H)。

¹³C NMR(151MHz，Chloroform-d)δ160.85，156.68，155.67，149.07，146.59，144.15，141.06，138.75，136.95，134.59，128.76，128.54，128.40，127.24，125.04，123.56，121.41，121.27，118.64，34.63。

HR-MS(ESI)calcd for C₂₃H₁₇N₂ ⁺[M+H]⁺321.1386 found 321.1383。

example 32: preparation of Compound 28

To a 10ml Schlenk tube were added 30.9mg of Compound 91(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 53% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 14.1mg of compound 28 (white solid, 49% yield). The obtained compound 28 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(600MHz，Chloroform-d)δ8.68(d，J＝4.7Hz，1H)，8.48(d，J＝7.9Hz，1H)，8.29(d，J＝1.8Hz，1H)，7.84(td，J＝7.7，3.9Hz，1H)，7.45(d，J＝1.9Hz，5H)，7.38-7.31(m，1H)，2.63(s，3H)，2.02(s，3H)。

¹³C NMR(151MHz，Chloroform-d)δ206.43，155.55，155.47，153.71，149.21，147.51，138.25，137.05，135.83，128.97，128.93，128.64，124.03，121.58，119.16，32.04，23.02。

HR-MS(ESI)calcd for C₁₉H₁₇N₂O⁺[M+H]⁺289.1335 found 289.1333。

example 33: preparation of Compound 30

To a 10ml Schlenk tube were added 25.4mg of Compound 92(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 61% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 13.5mg of compound 30 (white solid, 58% yield). The obtained compound 30 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(600MHz，Chloroform-d)δ8.70(dd，J＝4.7，1.5Hz，2H)，8.62(dd，J＝7.9，1.2Hz，2H)，8.45(dd，J＝7.8，1.1Hz，2H)，7.96(td，J＝7.8，1.1Hz，1H)，7.86(tt，J＝7.7，1.4Hz，2H)，7.33(ddt，J＝7.4，4.9，1.3Hz，2H)。

¹³C NMR(151MHz，Chloroform-d)δ156.22，155.32，149.12，137.95，136.93，123.79，121.22，121.05。

HR-MS(ESI)calcd for C₁₅H₁₂N₃ ⁺[M+H]⁺234.1026 found 234.1023。

example 34: preparation of Compound 33

To a 10ml Schlenk tube were added 35.6mg of Compound 93(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is 85 percent determined by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 27.1mg of compound 33 (pale yellow oily liquid, 81% yield). The obtained compound 33 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.73(dd，J＝4.9，1.7Hz，1H)，8.70(dt，J＝8.0，1.1Hz，1H)，8.59(ddd，J＝4.8，1.8，0.9Hz，1H)，8.32(s，1H)，7.78(td，J＝7.8，1.9Hz，1H)，7.53(dd，J＝7.6，1.7Hz，1H)，7.44-7.33(m，5H)，7.26-7.19(m，2H)，3.00-2.91(m，2H)，2.84(dd，J＝8.6，5.5Hz，2H)。

¹³C NMR(101MHz，Chloroform-d)δ156.08，154.69，152.09，151.49，149.89，148.92，148.80，138.73，136.96，135.87，134.13，131.83，128.90，128.45，128.19，123.72，123.64，122.19，122.12，27.60，24.98。

HR-MS(ESI)calcd for C₂₃H₁₈N₃ ⁺[M+H]⁺336.1495 found 336.1487。

example 35: preparation of Compound 35

To a 10ml Schlenk tube were added 38.6mg of Compound 94(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 99% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 35.0mg of compound 35 (white solid, 96% yield). The obtained compound 35 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.80-8.72(m，4H)，8.67(dq，J＝8.0，1.3Hz，2H)，7.88(ddt，J＝8.0，5.1，2.0Hz，4H)，7.56-7.49(m，2H)，7.36(ddt，J＝6.1，4.6，2.5Hz，2H)，1.38(s，9H)。

¹³C NMR(101MHz，Chloroform-d)δ156.33，155.80，152.32，150.17，149.08，136.94，135.48，127.03，125.89，123.79，121.42，118.80，34.74，31.33。

HR-MS(ESI)calcd for C₂₅H₂₄N₃ ⁺[M+H]⁺366.1965 found 366.1956。

example 36: preparation of Compound 37

To a 10ml Schlenk tube were added 33.1mg of Compound 95(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 95% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 28.2mg of compound 37 (white solid, 91% yield). The obtained compound 37 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.77(dd，J＝3.8，1.8Hz，4H)，8.73(d，J＝4.7Hz，2H)，8.67(d，J＝7.9Hz，2H)，7.94-7.86(m，2H)，7.82-7.77(m，2H)，7.41-7.35(m，2H)。

¹³C NMR(151MHz，Chloroform-d)δ156.42，155.73，150.48，149.22，147.49，146.09，137.03，124.16，121.76，121.41，118.70。

HR-MS(ESI)calcd for C₂₀H₁₅N₄ ⁺[M+H]+311.1291 found 311.1285。

example 37: preparation of Compound 39

To a 10ml Schlenk tube were added 32.0mg of Compound 96(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 78% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 23.0mg of compound 39 (white solid, 77% yield). The obtained compound 39 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results are as follows:

¹H NMR(600MHz，Chloroform-d)δ8.74(d，J＝4.8Hz，2H)，8.72(d，J＝1.6Hz，2H)，8.65(d，J＝7.9Hz，2H)，7.92-7.83(m，2H)，7.59(d，J＝2.1Hz，1H)，7.36(td，J＝5.5，2.8Hz，2H)，7.16-7.09(m，1H)，6.57(q，J＝2.2Hz，1H)。

¹³C NMR(151MHz，Chloroform-d)δ156.06，155.89，151.94，149.08，143.73，139.61，136.98，123.92，121.35，115.22，112.14，109.25。

HR-MS(ESI)calcd for C₁₉H₁₄N₃O⁺[M+H]+300.1131 found 300.1125。

example 38: preparation of Compound 43

To a 10ml Schlenk tube were added 34.4mg of Compound 97(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, the organic phase is combined and washed by saturated saline solution, after drying by anhydrous magnesium sulfate, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 93% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 28.7mg of Compound 43 (light oily liquid, 89% yield). The obtained compound 43 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.78-8.70(m，3H)，8.67(dd，J＝8.0，1.1Hz，1H)，8.45(d，J＝7.8Hz，1H)，7.95-7.83(m，3H)，7.75(t，J＝7.7Hz，1H)，7.52(dd，J＝8.3，6.5Hz，2H)，7.49-7.41(m，1H)，7.34(ddd，J＝7.5，4.8，1.2Hz，1H)，7.20(d，J＝7.6Hz，1H)，2.68(s，3H)。

¹³C NMR(101MHz，Chloroform-d)δ157.91，156.34，156.24，155.81，155.65，150.30，149.08，138.73，137.06，136.90，128.94，128.93，127.38，123.79，123.39，121.43，119.10，118.83，118.41，24.68。

HR-MS(ESI)calcd for C₂₂H₁₈N₃ ⁺[M+H]⁺324.1495 found 324.1488。

example 39: preparation of Compound 54

To a 10ml Schlenk tube were added 41.5mg of Compound 98(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmg @, 2.2 mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv @, 2), Co (dmg @BF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 97% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 33.8mg of compound 54 (pale yellow oily liquid, 89% yield). The obtained compound 54 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.70(d，J＝4.8Hz，1H)，8.55-8.45(m，2H)，8.01(d，J＝1.6Hz，1H)，7.82(td，J＝7.7，1.8Hz，1H)，7.76-7.68(m，2H)，7.49(t，J＝7.4Hz，2H)，7.43(dd，J＝8.4，6.3Hz，1H)，7.31(dd，J＝7.5，4.8Hz，1H)，6.81(d，J＝12.6Hz，1H)，6.44(d，J＝12.7Hz，1H)，2.08-2.01(m，2H)，1.76(dt，J＝11.9，7.0Hz，2H)，1.64-1.57(m，2H)，1.54(s，3H)1.12(d，J＝4.1Hz，6H)。

¹³C NMR(101MHz，Chloroform-d)δ156.93，156.47，155.96，149.04，148.90，138.76，136.87，135.64，133.24，131.83，129.19，129.01，128.85，126.88，123.63，121.47，120.40，116.67，39.37，34.99，32.33，28.46，21.22，19.35。

HR-MS(ESI)calcd for C₂₇H₂₉N₂ ⁺[M+H]⁺381.2325 found 381.2319。

example 40: preparation of Compound 60

Into a 10ml Schlenk tube were added 36.3mg of Compound 99(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is determined to be 95% by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 30.0mg of compound 60 (pale yellow oily liquid, 88% yield). The obtained compound 60 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.55(dd，J＝4.9，1.7Hz，1H)，8.43(d，J＝8.1Hz，1H)，7.96(s，1H)，7.73(td，J＝7.8，1.8Hz，1H)，7.39-7.27(m，5H)，7.19(q，J＝4.6Hz，1H)，3.25(dtd，J＝9.9，6.9，3.5Hz，1H)，2.84(q，J＝5.0Hz，1H)，2.72(pd，J＝6.9，4.7Hz，1H)，2.02-1.87(m，2H)，1.83-1.71(m，1H)，1.47-1.36(m，1H)，1.05(dd，J＝7.1，2.8Hz，3H)，0.76(d，J＝6.9Hz，6H)。

¹³C NMR(101MHz，Chloroform-d)δ159.37，151.76，150.69，148.90，140.55，136.90，136.14，128.69，128.24，128.05，127.49，123.30，121.23，119.96，45.76，32.04，29.33，28.42，21.78，21.63，19.21，18.62。

HR-MS(ESI)calcd for C₂₄H₂₇N₂ ⁺[M+H]⁺343.2169 found 343.2162。

example 41: preparation of Compound 65

53.9mg in a 10ml Schlenk tubeCompound 100(0.1mmol, 1equiv.), [ Ir (ppy)₂(bpy)]PF₆(0.002mmol), ammonium acetate (15.4mg, 0.2mmol, 2equiv.), Co (dmgBF2)2.2H2O₆(0.004mmol), DABCO (16.8mg, 0.15mmol, 1.5equiv.) and scandium triflate (9.8mg, 0.02mmol), evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under a stream of nitrogen. The reaction tube was placed under a 30W blue light for 24 hours, and after completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution was separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. times.2). Then, organic phase is combined and washed by saturated saline solution, anhydrous magnesium sulfate is dried, the organic phase is concentrated and added with dibromomethane as nuclear magnetic internal standard, and the reaction yield is 85 percent determined by nuclear magnetic hydrogen spectrum. Purification by column chromatography gave 42.5mg of compound 65 (white solid, 82% yield). The obtained compound 65 was subjected to hydrogen, carbon and mass spectrometric detection, with the following results:

¹H NMR(400MHz，Chloroform-d)δ8.66(ddd，J＝4.8，1.9，0.9Hz，1H)，8.52(dt，J＝8.0，1.1Hz，1H)，8.29(s，1H)，7.82(td，J＝7.7，1.8Hz，1H)，7.62-7.56(m，2H)，7.50-7.44(m，2H)，7.44-7.39(m，1H)，7.31-7.26(m，1H)，5.41(dt，J＝3.5，1.8Hz，1H)，4.68-4.55(m，1H)，2.88-2.67(m，2H)，2.45-2.31(m，3H)，2.16-2.08(m，1H)，2.04(s，3H)，1.96-1.84(m，3H)，1.81-1.72(m，2H)，1.72-1.60(m，4H)，1.14(d，J＝2.7Hz，6H)，0.86(tdd，J＝9.9，4.4，2.1Hz，2H)。

¹³C NMR(101MHz，Chlorofbrm-d)δ173.58，170.54，156.83，154.11，148.81，146.17，140.12，138.80，137.02，134.17，128.53，128.47，128.24，123.22，122.11，121.38，118.27，73.86，56.10，50.66，45.69，38.16，36.94，33.86，31.39，30.90，30.53，27.77，26.93，21.45，20.64，19.40，17.44。

HR-MS(ESI)calcd for C₃₅H₃₉N₂O₂ ⁺[M+H]⁺519.3006 found 519.2997。

while the methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention within the context, spirit and scope of the invention. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included within the invention.

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Method for synthesizing pyridine, bipyridine and terpyridine ligands

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