Preparation method of tetrahydropyridine molecules with photooxidation luminescence effect

Abstract

The invention relates to the field of luminescent materials, in particular to a preparation method and application of tetrahydropyridine molecules with a photooxidation luminescence effect. The invention mainly relates to a tetrahydropyridine molecular compound as shown in a formula I, a racemate, a stereoisomer or a tautomer of the tetrahydropyridine molecular compound, and a preparation method and application of the tetrahydropyridine molecular compound. According to the preparation method, asymmetric hybrid DA reaction is catalyzed, simple and cheap raw materials are taken as raw materials, the formula I is synthesized in one step under mild conditions, and the preparation method of the chiral molecule with the photooxidation luminescence effect is provided. The compound provided by the invention has an expected application prospect in the field of luminescence, especially in the field of photooxidation luminescence effect molecules. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of luminescent materials, and in particular to a preparation method and application of tetrahydropyridine molecules with photo-oxidation luminescence effect, in particular to a method for synthesizing tetrahydropyridine molecules by hetero-DA reaction. Background Art

[0002] Luminescence is a common phenomenon. The fluorescence phenomenon was discovered as early as 1575. Now, various luminescent materials have been widely used in the fields of light sources, optoelectronic devices, chemical sensors, biological probe preparation, and medical diagnosis. Luminescent materials can be divided into two categories: inorganic luminescent materials and organic luminescent materials. Among them, organic luminescent materials have strong molecular designability and luminescence performance adjustability, so they have attracted widespread attention from scientists. At present, most organic luminescent materials are rigid planar molecules with conjugated systems. Most of them are easily soluble in organic solvents and have high fluorescence quantum yields. However, they will aggregate in the aqueous phase and fluorescence quenching will occur. Aggregation fluorescence quenching (ACQ) phenomenon often limits the application of fluorescent materials. Tang Benzhong's research group first discovered the aggregation-induced emission (AIE) phenomenon in 2001. The fluorescence of the molecules is significantly enhanced in the aggregated state, which complements the aggregation fluorescence quenching phenomenon.

[0003] Although there are many molecules with luminescent effects in aqueous solvents, the preparation of these molecules, especially those with photo-oxidative luminescent reactions, is usually complicated and difficult to purify. The hetero-DA reaction refers to the asymmetric aza-Diels-Alder reaction, which can build molecular complexity and several consecutive stereo centers in one step. It is an efficient and atom-economical method for the synthesis of tetrahydropyridines, which are very frequent natural product skeletons and bio-related small molecules. The asymmetric hetero-DA reaction is an efficient and atom-economical method for the synthesis of tetrahydropyridines, which can build molecular complexity and multiple consecutive stereo centers in one step. Tetrahydropyridine is a very frequent natural product skeleton and bio-related small molecule. In the hetero-DA reaction, electron-rich dienes such as Danishefsky diene, Brassard diene and cyclopentadiene are usually required because their HOMO orbital energy levels are high enough to achieve reactions with dienophilic molecules. Simple unactivated dienes are rarely used due to their low price and abundant chemical raw materials, especially the application of the synthesis of chiral fluorescent molecules with photo-oxidative luminescence has not been reported. Summary of the invention

[0004] In view of the difficulties such as long synthesis steps in the current development of molecules with photo-oxidation luminescence effect, the present invention fills the gap in the field of hetero-DA reaction in the synthesis of molecules with photo-oxidation luminescence effect. A preparation method of photo-oxidation luminescence molecules is provided. A series of chiral molecules with photo-oxidation luminescence effect are designed and synthesized by hetero-DA reaction. The synthesis method can synthesize the target compound in one step. The preparation method is simple and easy, and a new mild synthesis method for synthesizing chiral molecules with photo-oxidation luminescence effect is opened up, and a new type of synthesis method of chiral molecules with photo-oxidation luminescence effect is added.

[0005] In order to solve the above technical problems, the present invention provides a tetrahydropyridine chiral molecule compound having a photo-oxidative luminescent effect as shown in the following formula I, and its racemate, stereoisomer or tautomer:

[0006]

[0007] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are the same or different, independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-10 Alkyl, C 1-10 Alkoxy, -NH 2 、-OC(O)C 1-10 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH) 2 ;

[0008] Every R a are the same or different and are independently selected from oxo (=O), -OH, halogen, -CN, -NO 2 、-NH 2 , C 1-10 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

[0009] According to an embodiment of the present invention, the compound of formula I has a structure shown in the following formula I',

[0010]

[0011] R 1 , R 2, R 3 , R 4 , R 5 , R 6 are the same or different, independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-10 Alkyl, C 1-10 Alkoxy, -NH 2 、-OC(O)C 1-10 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH) 2 ;

[0012] Every R a are the same or different and are independently selected from oxo (=O), -OH, halogen, -CN, -NO 2 、-NH 2 , C 1-10 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

[0013] As an example, the compound of formula I is selected from the following compounds MO:

[0014]

[0015] The present invention also provides a method for preparing the compound represented by formula I, comprising the following steps:

[0016]

[0017] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 Has the same definition as above.

[0018] According to an embodiment of the present invention, the catalyst of the reaction is composed of boron Lewis acid and chiral phosphoric acid, wherein the boron Lewis acid is selected from one or more of boron trifluoride, boron trichloride, boron tribromide, triphenylboron and trispentafluorophenylboron; the amount of the catalyst is 1-100%.

[0019] According to an embodiment of the present invention, the solvent of the reaction can be dichloromethane, chloroform, tetrahydrofuran, methanol, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, ether, ethyl acetate, anisole, toluene, xylene compounds, trifluorotoluene or mesitylene;

[0020] According to an embodiment of the present invention, the reaction temperature is room temperature or -40°C; the reaction time can be 12 to 72 hours.

[0021] Definition and explanation of terms

[0022] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be arbitrarily combined and combined with each other. The group definitions and compound structures after such combination and combination shall fall within the scope recorded in the specification of this application.

[0023] "More" means more than three.

[0024] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0025] The term "C 1-10 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having about 40 carbon atoms. For example, "C 1-6 The term “alkyl” refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl or the like or isomers thereof.

[0026] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 20 carbon atoms, preferably "C 3-10 The term "Cycloalkyl" 3-10 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or a bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

[0027] The term "3-20 membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane, which contains 1-5 heteroatoms independently selected from N, O and S, and the total number of ring atoms is 3-20 (such as 3, 4, 5, 6, 7, 8, 9, 10, etc.), and is preferably a "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane, which contains 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl may be attached to the rest of the molecule through any of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to, a 4-membered ring, such as azetidinyl, oxetanyl; a 5-membered ring, such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring, such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, such as, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta [c] pyrrole-2 (1H) -yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo [1,2-a] pyrazine-2 (1H) -yl ring. The ring containing the nitrogen atom may be partially unsaturated, i.e. it may contain one or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as but not limited to dihydroisoquinolinyl. According to the present invention, the heterocyclic group is non-aromatic. When the 3-20-membered heterocyclic group is connected with other groups to form the compound of the present invention, the carbon atom on the 3-20-membered heterocyclic group may be connected with other groups, or the heterocyclic atom on the 3-20-membered heterocyclic group may be connected with other groups. For example, when the 3-20-membered heterocyclic group is selected from piperazinyl, the nitrogen atom on the piperazinyl may be connected with other groups. Or when the 3-20-membered heterocyclic group is selected from piperidinyl, the nitrogen atom on the piperidinyl ring and the carbon atom on the para position thereof may be connected with other groups.

[0028] The term "C 6-20 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-11 The term "C 6-11The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-11 Aryl), especially a ring having 6 carbon atoms ("C 6 aryl), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 11 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0029] The term "5-20 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like. When the 5-20 membered heteroaryl is connected to other groups to form the compound of the present invention, the carbon atom on the 5-20 membered heteroaryl ring may be connected to other groups, or the heteroatom on the 5-20 membered heteroaryl ring may be connected to other groups. When the 5-20 membered heteroaryl is substituted, it may be monosubstituted or polysubstituted. In addition, there is no limitation on the substitution site, for example, the hydrogen connected to the carbon atom on the heteroaryl ring may be substituted, or the hydrogen connected to the heteroatom on the heteroaryl ring may be substituted.

[0030] Unless otherwise specified, heterocyclic groups, heteroaryls or heteroarylene groups include all possible isomeric forms thereof, such as positional isomers thereof. Thus, for some illustrative non-limiting examples, forms substituted or bonded to other groups at one, two or more positions of the 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-positions, etc. (if present), may include pyridin-2-yl, pyridin-2-ylene, pyridin-3-yl, pyridin-3-ylene, pyridin-4-ylene and pyridin-4-ylene; thienyl or thienylene groups include thien-2-yl, thien-2-ylene, thien-3-ylene and thien-3-ylene; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl.

[0031] Unless otherwise stated, the definitions of terms herein also apply to groups containing the term, e.g. 1-10 The definition of alkyl also applies to C1-10 Alkoxy, etc.

[0032] Beneficial Effects

[0033] Compared with the prior art, the advantages and positive effects of the present invention are:

[0034] The present invention successfully prepares tetrahydropyridine chiral molecules with photo-oxidation luminescence effect, the preparation process is simple, and has the following advantages:

[0035] First, the tetrahydropyridine chiral molecules prepared by the hetero-DA asymmetric reaction of substituted 1H-quinoxaline-2-one or substituted 2H-1,4-benzoxazine-2-one and substituted 1,4-butadiene have excellent photo-oxidation luminescence effect.

[0036] Second, the preparation method disclosed in the present invention has a simple synthesis process, few reaction steps, low cost and can prepare tetrahydropyridine chiral molecules with photo-oxidation luminescence effect under mild conditions.

[0037] Third, the preparation method disclosed in the present invention successfully introduces the catalytic asymmetric hetero-DA reaction into the field of preparing chiral molecules with photo-oxidation luminescence effect, broadening the preparation method of chiral molecular materials with photo-oxidation luminescence effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0039] Figure 1 The ultraviolet spectrum of the product ethanol solution of the specific embodiment 2 of the present invention;

[0040] Figure 2 The UV spectrum of the product of the second specific embodiment of the present invention in ethanol / water (1:9) solution;

[0041] Figure 3 Fluorescence spectrum of the product of specific embodiment 2 of the present invention in ethanol solution;

[0042] Figure 4 Fluorescence spectrum of the product of the second specific embodiment of the present invention in ethanol / water (1:9) solution;

[0043] Figure 5 The fluorescence spectra of the product of the second specific embodiment of the present invention in ethanol and ethanol / water (1:9) solution respectively;

[0044] Figure 6 Circular dichroism spectrum of the product of specific embodiment 2 of the present invention in ethanol solution;

[0045] Figure 7 Circular dichroism spectrum of the product of specific example 2 of the present invention in ethanol / water (1:9) solution. DETAILED DESCRIPTION

[0046] In order to make the purpose, technical scheme and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the examples described herein are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.

[0047] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0048] Example 1: Preparation of chiral compounds

[0049]

[0050] Use B(C 6 D 5 ) 3 The / CPA catalytic system is used as a catalyst to catalyze the asymmetric hetero-DA reaction at room temperature with 1-methylquinoxaline-2(1H)-one (1.0 equiv.) and 2,3-dimethylbutadiene (2.0 equiv.) as substrates. The reaction equation is as above. 6 F 5 ) 3 and chiral phosphoric acid (S)-A are added to a reaction tube, and then the substrate and reaction solvent are added in sequence, stirred at room temperature, and the reaction is monitored by thin layer chromatography. The amount of the catalyst can be reduced to 2 mol%, and petroleum ether and ethyl acetate are used as flushing agents, and column chromatography separation on a silica gel column is directly performed to obtain the target product with a yield of 80% and an enantioselectivity of 99:1.

[0051] 1 H NMR (400 MHz, CDCl 3 )δ7.03 (t, J=7.6Hz, 1H), 6.93 (d, J=7.6Hz, 1H), 6.87 (t, J=7.6Hz, 1H), 6.75 (d, J= 8.1Hz, 1H), 3.86-3.72(m, 2H), 3.46-3.32(s, 4H), 2.56-2.34(m, 2H), 1.71(s, 6H); 13 C NMR (101 MHz, CDCl 3)δ168.06, 136.41, 129.19, 124.21, 123.90, 121.70, 119.30, 114.07, 112.12, 56.33, 51.56, 33.81, 28.97, 18.38, 16.12; HRMS(EI)calcdfor C 15 H 18 N 2 O[M + ]: 242.1419, found: 242.1414; HPLC: Daicel Chiralpak IC, n-hexane / i-PrOH=3:1, Flow rate=1.0mL / min, λ=210nm, t R =9.5min(major)and t R =10.2min(minor).

[0052] Example 2: Testing of the Luminescence Performance of Chiral Compounds

[0053] The target product was prepared to a concentration of 10 -1 M ethanol solution and ethanol / water solution with a volume ratio of 1:9, and then measured the changes of UV spectrum, fluorescence spectrum and circular dichroism spectrum over time. The UV spectrum of the sample shows that the intensity of UV absorption first increases and then decreases with the illumination, but the absorption signal of the mixed solution sample does not change as much as that of the pure ethanol solution sample, and the samples all have new absorption signals near 365nm and 226nm ( Figure 1 and Figure 2) The fluorescence spectrum of the sample shows that the intensity of the fluorescence emission first increases and then decreases with the illumination, but the fluorescence emission intensity of the mixed solution sample does not change as much as that of the pure ethanol solution sample. The maximum emission wavelength of the pure ethanol solution sample is around 480nm ( Figure 3) , while the maximum emission wavelength of the mixed solution sample blue-shifted to around 470nm ( Figure 4) , the fluorescence of the mixed solution sample is stronger than that of the pure ethanol solution sample ( Figure 5) The circular dichroism spectra of the samples show that the asymmetric absorption signal of the samples gradually weakens with illumination, and the asymmetric absorption signal of the mixed solution sample changes faster than that of the pure ethanol solution sample ( Figure 6 and Figure 7) .

[0054] Example 3: Mechanism of luminescence of chiral compounds

[0055]

[0056] Take an appropriate amount of the target product and dissolve it in dichloromethane, place it under 365nm ultraviolet light, and then use heavy water for extraction. The product extracted with heavy water is directly subjected to nuclear magnetic resonance analysis and high-resolution mass spectrometry analysis. According to the results, it is inferred that the product will be oxidized under 365nm light to generate the corresponding salt.

[0057] 1 H NMR (600 MHz, D 2 O) δ9.66 (s, 1H), 8.79 (s, 1H), 8.49 (d, J = 8.7Hz, 1H), 7.82 (t, J = 7.9Hz, 1H), 7.76 (d, J=8.5Hz, 1H), 7.59 (t, J=7.9Hz, 1H), 3.77 (s, 3H), 2.68 (s, 3H), 2.60 (s, 3H); 13 C NMR (151 MHz, D 2 O) δ159.85, 155.08, 141.92, 135.14, 134.22, 132.65, 131.55, 127.84, 125.72, 122.71, 117.69, 117.50, 30.53, 19.85, 16.71; HRMS(EI)calcd forC 15 H 15 N 2 O[M + ]: 239.1179, found: 239.1178.

[0058] The above is an exemplary description of the embodiments of the present invention. However, the protection scope of the present invention is not limited to the above specific embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. The compound represented by formula I, its racemate, stereoisomer or tautomer: in, R1, R2, R3, R4, R5, R6 are the same or different, independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted with one, two or more R a Substituted with the following groups: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2; Every R a are the same or different and are independently selected from oxo (=O), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

2. The compound according to claim 1, characterized in that The compound of formula I has the structure shown in the following formula I', Wherein, R1, R2, R3, R4, R5, R6 are the same or different, independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2; Every R a are the same or different and are independently selected from oxo (=O), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 Aryl or 5-20 membered heteroaryl.

3. The compound according to claim 1 or 2, characterized in that The compound of formula I is selected from the following compounds M0:

4. A method for preparing the compound according to any one of claims 1 to 3, characterized in that: The steps include: Wherein, R1, R2, R3, R4, R5, and R6 have the definitions as described in any one of claims 1-3.

5. The method according to claim 4, characterized in that The reaction is a catalytic asymmetric hetero DA reaction; the catalyst of the reaction is composed of boron Lewis acid and chiral phosphoric acid, wherein the boron Lewis acid is selected from one or more of boron trifluoride, boron trichloride, boron tribromide, triphenylboron and trispentafluorophenylboron; the amount of the catalyst is 1-100%.

6. The catalytic asymmetric hetero-DA reaction according to claim 4, characterized in that First, one or more of boron trifluoride, boron trichloride, boron tribromide, triphenylboron and tripentafluorophenylboron and chiral phosphoric acid are added to a reaction tube, and then the substrate and reaction solvent are added in sequence, and the mixture is stirred at room temperature or -40°C, and the reaction is monitored by thin layer chromatography.

7. A composition having photo-oxidative luminescence, characterized in that: The compound comprises at least one of the compound according to any one of claims 1 to 3, its racemate, stereoisomer or tautomer. The target product is prepared into a concentration of 10 -4 It was found that the intensity of the fluorescence emission curve gradually changed with the increase of illumination time, showing a good luminescence effect, and the signal of asymmetric absorption of chiral molecules would also change.

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