Transannular axially chiral indolizine compounds, methods of preparation and uses

Abstract

The application discloses a transannular chiral indolizine compound (I) and a preparation method and application thereof. The structure of the compound of formula I is as follows: wherein R 1 , R 2 , R 3 , R 4 and Ar are defined in the description. The compound of the application shows significant circularly polarized luminescence performance, and a g lum value is as high as 0.01, which shows great application potential in chiral organic optoelectronic materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic light-emitting materials and organic electroluminescent devices, and particularly relates to a cross-axial chiral indolizine compound light-emitting material, which has high light-emitting efficiency and axial chiral circularly polarized emission characteristics; when applied to an organic electroluminescent device, a high-efficiency circularly polarized electroluminescent device can be obtained. BACKGROUND

[0002] As a research hotspot in the field of organic electronics, the development of new OLED materials is still in full swing, especially the urgent development of next-generation new light-emitting materials and special-purpose OLED devices. Among them, OLED devices prepared with chiral light-emitting materials as the light-emitting center can directly emit circularly polarized electroluminescence, i.e., circularly polarized organic light-emitting diodes, avoiding complex optical filtering structures and brightness efficiency loss, which will have great application prospects in the fields of 3D display and optoelectronic communication, and also provides a new research direction for the development of next-generation OLED materials and devices.

[0003] Chiral light-emitting materials can generally be divided into conjugated high molecular polymers, phosphorescent metal complexes and organic small molecules. Among them, circularly polarized-thermally activated delayed fluorescence (CP-TADF) materials are considered as a new type of light-emitting material with great development potential due to their circularly polarized luminescence and 100% light utilization characteristics, and have important applications in optical storage, optical anti-counterfeiting, 3D display and other aspects.

[0004] At present, most CP-TADF molecules adopt the "chiral perturbation" strategy, that is, through chiral sources such as covalent linkage carbon chirality, axial chirality or face chirality, circularly polarized luminescence is realized. However, in these "chiral perturbation" strategies, the chiral source does not participate in the electronic arrangement of the molecular frontier orbital, resulting in a generally small material asymmetry factor (g lum ). Therefore, it is crucial to develop high-efficiency light-emitting materials with coinciding chiral source and light-emitting center and their devices.

[0005] Aromatic compounds with multiple chiral axes are a class of organic compounds with multiple chiral axes and containing aromatic ring structures, which have important application values in the fields of natural product synthesis, drug chemistry, functional materials, etc.

[0006] The ortho-1,2-biaxial aromatic molecules are a subclass of multi-axial aromatic compounds, and the aromatic compounds with ortho-1,2-biaxial chirality are a ubiquitous structural motif in the synthesis of important substances. As an important class of aromatic fused heterocyclic compounds, indolizine has an equal important position with indole in synthetic chemistry. At present, great progress has been made in the design and synthesis of functional small molecules containing indolizine heterocycle, but unfortunately, compared with the frequent use of axially chiral indole molecules, the development of enantioselective construction methods of axially chiral indolizine compounds is still limited. There is little report on the application of cross-ring axially chiral indolizine compounds as light-emitting materials in the prior art.

[0007] In addition, the stereoselective restriction on the ortho-1,2-biaxial chiral center by kinetic control limits the synthesis of such compounds, so the existing research mainly focuses on the synthesis of the same-ring ortho-1,2-biaxial chiral molecules.

[0008] The fused ring aromatic hydrocarbons with cross-ring ortho-1,2-biaxial arrangement provide a diversification strategy for preparing various cross-ring biaxial chiral structures, and exhibit different properties and functions due to their unique topological structure.

[0009] However, it will be more complex and challenging to achieve stereoselective control of cross-ring biaxial chiral biaryl compounds than the same-ring variants, and there is no literature report at present. SUMMARY

[0010] The primary purpose of the present application is to provide a cross-ring axially chiral indolizine compound light-emitting material and a preparation method thereof, which can be used as a light-emitting center and applied in an organic electroluminescent device.

[0011] The present application provides a cross-ring axially chiral indolizine compound represented by formula I and stereoisomers thereof,

[0012]

[0013] R 1 selected from acetyl allyl or benzoyl;

[0014] R 2 selected from H, C1-C6 alkyl or phenyl;

[0015] R 3 selected from H, C1-C6 alkyl or phenyl;

[0016] R 4 selected from C1-C6 alkyl,

[0017] R 5 selected from phenyl, phenethyl or naphthyl;

[0018] Ar selected

[0019] R is selected from H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-C1-C6 alkoxy, C1-C6 alkylthio, halogen, TBSO-C1-C6 alkyl, ester, halo-C1-C6 alkyl, C2-C6 alkenyl, substituted C2-C6 alkenyl, C2-C6 ynyl, substituted amino, phenyl, naphthyl, or benzoynyl optionally substituted with one or more substituents;

[0020] n is a natural number between 0 and 3.

[0021] This invention also proposes a method for synthesizing transcyclic chiral indazine compounds, comprising the following steps: Compound II is synthesized into compound I in the presence of a catalyst and a chiral ligand, and the synthetic route is as follows:

[0022]

[0023] in,

[0024] R 1 R 2 R 3 R 4 Ar is defined as described above;

[0025] The catalyst is selected from metal catalysts, preferably copper catalysts, and more preferably tetrafluoroborate tetra(acetonitrile) copper catalysts as metal catalysts;

[0026] The ligand is selected from chiral bisoxazoline ligands and chiral phosphine ligands, preferably chiral bisarylphosphine ligands, and more preferably S-(-)-1,1′-binaphthyl-2,2′-bisdiphenylphosphine.

[0027] The catalyst used in the above reaction is selected from metal catalysts, preferably copper catalysts, and more preferably tetra(acetonitrile)copper tetrafluoroborate.

[0028] The present invention also provides an organic electroluminescent display containing the above-described transcyclic chiral indazine compound as an organic light-emitting material.

[0029] The beneficial effects achieved by this invention are as follows:

[0030] 1. The transcyclic axial chiral indazine compound luminescent material of the present invention has the advantages of high luminous efficiency and stable chemical properties. In addition, the material of the present invention has a large steric hindrance on its periphery, which effectively suppresses molecular stacking and improves luminous efficiency. On the other hand, the transcyclic axial chiral indazine compound has circularly polarized luminescence properties.

[0031] 2、The application uses pyridine compounds as substrates, and through catalyst catalysis, a simple, safe, efficient and universal synthesis method for constructing cross-cyclic axis chiral indolizine compounds in one step is provided, and the yield is high and the ee value is high.

[0032] 3、The catalyst used in the application is cheap and easy to obtain, environment-friendly, green and safe.

[0033] 4、The reaction condition of the application is easy to control, the reaction is mild, and the side reaction is less. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 Circularly polarized luminescence spectra of compounds 2a, 4a, 4e and 4ac.

[0035] Figure 2 Luminescence asymmetric factor (g lum ) spectrum of compounds 2a, 4a, 4e and 4ac. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. Unless otherwise explicitly indicated, in the entire specification and claims, the term "comprise" or its variants such as "include" or "comprise" and the like will be understood as including the stated components or steps, and excluding other components or steps.

[0037] In addition, in order to better illustrate the present application, numerous specific details are given in the specific embodiments below.

[0038] Those skilled in the art should understand that the present application can also be implemented without certain specific details. In some embodiments, the raw materials, methods, means and the like which are well known to those skilled in the art are not described in detail, in order to highlight the main idea of the present application.

[0039] The term "alkyl" (and in alkyl moieties of other groups containing alkyl groups, such as alkoxy groups, moieties of haloalkyl groups, alkyl moieties of arylalkyl groups) as used herein denotes in each case straight-chain or branched alkyl groups having usually from 1 to 20 carbon atoms, often from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 3 carbon atoms. Examples of C1-C4alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethyl- ethyl (tert-butyl). Examples of C1-C6alkyl groups are, in addition to the groups mentioned under C1-C4alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.

[0040] When a group is substituted, the substituents can be alkyl, halogen, cyano, nitro, heterocyclyl, amido, ester, alkoxy and aryl, but are not limited thereto, for example, when alkyl is substituted, haloalkyl is formed, but is not limited thereto, wherein the carbon atom of the alkyl group can be replaced by other atoms or groups.

[0041] In the present application, halogen is usually fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. Correspondingly, this also applies to halogen in combination with other structures, such as haloalkyl. Haloalkyl preferably has a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. Examples of haloalkyl are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, difluorochloromethyl and dichlorofluoromethyl.

[0042] In the present application, "C1-C6alkylthio" means straight-chain or branched alkylthio groups having 1 to 6 carbon atoms, examples being methylthio, ethylthio, propylthio and the like, but are not limited thereto.

[0043] The present application first provides a trans-fused-axial chiral indolizine compound represented by formula I and stereoisomers thereof,

[0044]

[0045] R 1 is selected from H, C1-C6 alkyl or phenyl; allyl; or benzoyl;

[0046] R 2 is selected from H, C1-C6 alkyl or phenyl;

[0047] R 3 is selected from H, C1-C6 alkyl or phenyl;

[0048] R 4 is selected from C1-C6 alkyl,

[0049] R 5 is selected from phenyl, phenethyl or naphthyl;

[0050] Ar is selected from

[0051] R is selected from H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-C1-C6 alkoxy, C1-C6 alkylthio, halogen, TBSO-C1-C6 alkyl, ester, halogenated C1-C6 alkyl, C2-C6 alkenyl, substituted C2-C6 alkenyl, C2-C6 alkynyl, substituted amine, phenyl optionally substituted with one or more substituents, naphthyl or phenacryl;

[0052] n is a natural number from 0 to 3.

[0053] In particular, the compound of the present application is selected from the following compounds:

[0054]

[0055]

[0056]

[0057]

[0058] In a second aspect of the present application, a method for synthesizing the compound of the present application is provided, which comprises the following steps: synthesizing a compound of formula II in the presence of a catalyst and a chiral ligand to obtain a compound of formula I, and the synthetic route is as follows:

[0059]

[0060] wherein,

[0061] R 1 , R 2 , R 3 , R4 and Ar are defined as above;

[0062] The catalyst is selected from metal catalysts, preferably copper catalysts, more preferably tetrakis(acetonitrile)copper tetrafluoroborate is the metal catalyst;

[0063] The ligand is selected from chiral bisoxazoline ligands, chiral phosphine ligands, preferably chiral bisaryl phosphine ligands, more preferably S-(-)-1,1'-binaphthalene-2,2'-bis(diphenylphosphine).

[0064] In the above synthesis method, the molar ratio of the catalyst: ligand of formula II is 1: 0.03-0.1: 0.036-0.12, preferably: 1: 0.06: 0.072.

[0065] In the above synthesis method, the reaction temperature is -10°C-85°C, preferably 0°C-30°C, more preferably 0°C-10°C.

[0066] The present application will be further described in conjunction with the following examples, but the present application is not limited to the following examples. Simple substitutions or improvements made by those skilled in the art to the present application shall fall within the scope of the technical solutions protected by the present application. The reagents in the examples of the present application can be purchased from the market if not specifically mentioned.

[0067] Synthesis of compound 2a in Example 1

[0068] In a 10 mL vacuum tube, compound 1a (52 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), ligand L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), nitrogen replacement three times, 0°C reaction, TLC detection of reaction to complete, vacuum concentration to dryness, then column chromatography separation to obtain 44 mg of target compound 2a, yield 85%, ee value 95%.

[0069] The results are as follows by NMR detection:

[0070] 1H NMR (400 MHz, CDC13) δ 7.68 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.42 (dd, J = 8.8, 1.6 Hz, 2H), 7.29 - 7.24 (m, 2H), 7.18 - 7.14 (m, 3H), 6.92 (d, J = 2.8 Hz, 1H), 6.82 (dd, J = 8.8, 2.8 Hz, 1H), 6.74 (dd, J = 8.8, 6.4 Hz, 1H), 6.68 (s, 1H), 6.29 (dd, J = 6.4, 1.6 Hz, 1H), 6.08 (d, J = 9.2 Hz, 1H), 5.89 (d, J = 9.2 Hz, 1H), 3.68 (s, 3H), 2.74 (s, 3H), 2.58 (s, 3H), 2.32 (s, 3H).

[0071] 13 C NMR (101 MHz, CDC13) δ 169.27, 157.49, 155.39, 154.15, 135.73, 133.32, 131.52, 129.98, 128.85, 128.58, 127.84, 127.25, 127.20, 125.76, 125.68, 124.68, 123.49, 122.69, 117.18, 116.61, 115.65, 115.48, 115.35, 115.08, 114.95, 110.08, 109.59, 107.91, 104.37, 55.09, 54.57, 54.22, 21.03.

[0072]

[0073] Synthesis of compound 2a in example 2-19

[0074] Compound 2a was synthesized according to the method of example 1-19 by changing the relevant reaction conditions to investigate the effect of the reaction, and the results are shown in table 1

[0075] Table 1 Effect of reaction conditions on the synthesis of compound 2a

[0076]

[0077]

[0078] The specific operation of examples 20-21 is the same as that of example 1, only the equivalent of the catalyst and ligand is changed, and the results are as follows:

[0079] Table 2 Effect of catalyst and ligand equivalent on the yield of synthesis of compound 2a

[0080] Serial number Raw material equivalent Catalyst equivalent Ligand equivalent Yield 20 1.0 0.03 0.036 87％ 21 1.0 0.1 0.12 94％

[0081] Synthesis of compound 2b

[0082]

[0083] In a 10 mL vacuum tube, compound 1b (57 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), ligand L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), nitrogen replacement three times, 0 °C reaction, TLC detection reaction to complete, vacuum concentration to dryness, then column chromatography separation to obtain 51 mg of target compound 2b, yield 90%, ee value 93%.

[0084] The results are as follows by NMR detection:

[0085] 1 H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 1.6 Hz, 1H), 7.76 (d, J = 8.8 Hz, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.51 (dd, J = 9.2, 1.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 7.36 - 7.28 (m, 4H), 7.26 - 7.22 (m, 1H), 6.83 (dd, J = 6.4, 8.8 Hz, 1H), 6.74 (s, 1H), 6.36 (dd, J = 1.2, 6.4 Hz, 1H), 6.14 (d, J = 3.2 Hz, 1H), 6.12 (d, J = 2.8 Hz, 1H), 2.95 (s, 3H), 2.74 (s, 3H), 2.40 (s, 3H).

[0086] 13 C NMR (101 MHz, CDCl3) δ 168.92, 155.69, 154.17, 135.48, 133.26, 131.40, 130.03, 129.07, 128.72, 128.36, 127.85, 127.43, 127.25, 126.15, 125.99, 125.71, 124.77, 122.78, 120.22, 117.22, 115.73, 115.42, 115.31, 110.77, 110.16, 109.61, 54.67, 54.47, 21.06.

[0087] Synthesis of compound 2c

[0088]

[0089] In a 10 mL vacuum tube, compound 1c (52 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), ligand L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), nitrogen replacement three times, 0 °C reaction, TLC detection reaction to complete, vacuum concentration to dryness, then column chromatography to obtain 48 mg of target compound 2c, yield 92%, ee value 96%.

[0090] NMR detection results are:

[0091] 1 H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.4 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 7.46 (d, J = 8.4 Hz, 1H), 7.43 - 7.40 (m, 2H), 7.27 - 7.23 (m, 2H), 7.20 (d, J = 8.8 Hz, 1H), 7.17 - 7.13 (m, 1H), 7.02 (dd, J = 1.6, 8.4 Hz, 1H), 6.72 (dd, J = 8.8, 6.4 Hz, 1H), 6.67 (s, 1H), 6.27 (dd, J = 1.2, 6.4 Hz, 1H), 5.99 (dd, J = 16, 9.2 Hz, 2H), 2.64 - 2.59 (m, 5H), 2.54 (s, 3H), 2.31 (s, 3H), 1.16 (t, J = 7.6 Hz, 3H).

[0092] 13 C NMR (101 MHz, CDCl3) δ 169.09, 154.93, 154.05, 141.07, 134.42, 133.35, 131.52, 129.94, 128.83, 127.82, 127.24, 127.21, 127.03, 126.44, 125.78, 125.62, 124.55, 124.08, 123.66, 122.66, 117.26, 116.52, 115.37, 115.25, 115.15, 110.04, 109.59, 109.44, 54.40, 54.20, 29.24, 21.04, 15.31.

[0093] Synthesis of compound 2d of Example 24

[0094]

[0095] In a 10 mL vacuum tube, add compound 1d (56 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), ligand L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), replace with nitrogen for three times, react at 0 °C, TLC test the reaction until the raw material is completely reacted, vacuum concentration to dryness, and then separate by column chromatography to obtain 48 mg of target compound 2d, yield 85%, ee value is 96%.

[0096] The results are as follows by NMR detection:

[0097] 1 H NMR (400 MHz, CDCl3) δ 7.92 (t, J = 1.2 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.66 - 7.63 (m, 3H), 7.52 (td, J = 1.6, 8.4 Hz, 1H), 7.44 - 7.39 (m, 2H), 7.37 - 7.23 (m, 5H), 6.83 - 6.79 (m, 2H), 6.35 (dd, J = 1.6, 6.4 Hz, 1H), 6.14 (dd, J = 7.6, 9.2 Hz, 2H), 2.68 (s, 3H), 2.64 (s, 3H), 2.40 (s, 3H).

[0098] 13 C NMR (101 MHz, CDCl3) δ 169.01, 155.27, 154.17, 141.23, 137.69, 134.59, 133.39, 131.48, 130.03, 128.86, 128.82, 127.87, 127.69, 127.39, 127.26, 127.18, 127.11, 127.08, 125.81, 125.70, 124.69, 124.11, 122.76, 122.14, 117.31, 116.26, 116.11, 115.51, 115.31, 115.26, 110.44, 110.20, 109.77, 54.38, 54.33, 21.09.

[0099] Based on the above reaction conditions and operations of Examples 22-24, only the substrates are changed to obtain the following compounds in Table 2:

[0100] Table 3 Compounds prepared from different substrates

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] Synthesis of compound 4a

[0107]

[0108] In a 10 mL vacuum tube, compound 3a (44 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), nitrogen replacement three times, 10 °C reaction, TLC detection of reaction to complete, vacuum concentration to dryness, then column chromatography to obtain 31 mg of target compound 4a, yield 71%, ee value 96%.

[0109] The results were detected by NMR:

[0110] 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.8 Hz, 1H), 7.33 (dd, J = 4.8, 8.8 Hz, 2H), 7.15 (s, 1H), 6.94 (d, J = 2.8 Hz, 2H), 6.86 (dd, J = 2.4, 8.8 Hz, 1H), 6.83 (s, 1H), 6.71 (dd, J = 2.4, 15.2 Hz, 2H), 6.40 (d, J = 8.8 Hz, 2H), 6.26 (d, J = 6.8 Hz, 1H), 6.07 (t, J = 7.6 Hz, 1H), 3.68 (s, 3H), 3.46 (s, 3H), 2.30 (s, 3H).

[0111] 13 C NMR (101 MHz, CDCl3) δ 169.10, 158.50, 154.86, 137.41, 135.01, 134.80, 129.26, 129.22, 127.82, 127.48, 127.40, 127.00, 126.22, 125.18, 124.65, 124.08, 116.55, 116.02, 115.88, 115.53, 114.89, 113.93, 110.16, 108.78, 102.95, 55.17, 54.99, 20.98.

[0112] Synthesis of compound 4e

[0113]

[0114] In 10 mL vacuum tube, add compound 3e (60 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), replace with nitrogen for three times, 10 °C reaction, TLC detection reaction to complete, vacuum concentration to dryness, then column chromatography to obtain 44 mg of target compound 4e, yield 74%, ee value 92%.

[0115] The results are as follows by NMR detection:

[0116] 1 H NMR (400 MHz, CDCl3) δ 7.66 (d, J = 8.8 Hz, 1H), 7.62 (d, J = 8.8 Hz, 1H), 7.39 (dd, J = 1.2, 8.8 Hz, 1H), 7.24 - 7.19 (m, 4H), 7.12 (dd, J = 2.0, 8.0 Hz, 1H), 7.02 (d, J = 2.4 Hz, 1H), 6.99 (t, J = 7.2 Hz, 2H), 6.93 (dd, J = 2.4, 8.8 Hz, 1H), 6.89 - 6.86 (m, 4H), 6.78 - 6.73 (m, 2H), 6.70 (dd, J = 2.4, 8.0 Hz, 1H), 6.44 (dd, J = 2.0, 8.4 Hz, 1H), 6.35 (dd, J = 1.6, 6.8 Hz, 1H), 5.99 (dd, J = 2.0, 8.4 Hz, 1H), 3.72 (s, 3H), 3.59 (s, 3H), 2.38 (s, 3H).

[0117] 13 C NMR (101 MHz, CDCl3) δ 169.07, 158.52, 154.93, 147.31, 146.89, 137.22, 134.75, 129.50, 129.24, 129.15, 129.03, 128.48, 127.74, 127.49, 124.72, 124.25, 124.05, 122.79, 121.48, 120.34, 116.59, 116.18, 116.13, 115.89, 114.63, 113.82, 110.20, 108.95, 103.04, 55.21, 55.15, 21.02.

[0118] Synthesis of compound 4ac of example 43

[0119]

[0120] In a 10 mL vacuum tube, add compound 3ac (51 mg, 0.1 mmol, 1.0 eq.), Cu(MeCN)4BF6(1.9 mg, 0.006 mmol), L7 (4.5 mg, 0.0072 mmol), DCM (1 mL), replace with nitrogen for three times, 10 °C reaction, TLC detection reaction to complete, vacuum concentration to dryness, then column chromatography to obtain 45 mg of target compound 4ac, yield 88%, ee value 90%.

[0121] The results are as follows by NMR detection:

[0122] 1 H NMR (400 MHz, CDCl3) δ 7.60 - 7.53 (m, 3H), 7.48 - 7.39 (m, 4H), 7.30 (d, J = 7.2 Hz, 1H), 7.05 (d, J = 2.4 Hz, 2H), 6.95 (dd, J = 2.4, 8.8 Hz, 1H), 6.81 (t, J = 7.6 Hz, 1H), 6.76 (s, 1H), 6.65 (d, J = 6.8 Hz, 1H), 6.53 (dd, J = 8.0, 13.6 Hz, 2H), 6.40 (d, J = 6.8 Hz, 1H), 6.18 (t, J = 7.6 Hz, 1H), 3.78 (s, 3H), 3.60 (s, 3H), 1.68 (s, 3H).

[0123] 13 C NMR (101 MHz, CDCl3) δ 169.74, 158.54, 154.79, 138.72, 136.69, 135.12, 134.85, 131.02, 129.37, 129.29, 127.98, 127.78, 127.64, 127.42, 127.22, 127.01, 126.28, 125.23, 124.10, 122.95, 118.10, 117.50, 115.88, 115.62, 113.85, 111.52, 108.83, 103.05, 55.24, 55.05, 20.19.

[0124] Based on the reaction conditions and operations of the above Examples 41-43, only the substrates are changed to obtain the compounds in Table 3 as follows:

[0125] Table 4 Compounds prepared with different substrates

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] Test example

[0134] 1. Determination of Circularly Polarized Luminescence Spectra and Luminescence Asymmetry Factor (g lum ) Spectra

[0135] 2a, 4a, 4e, 4ac compounds were taken 6.5 mg, 5.5 mg, 7.6 mg, 6.4 mg respectively, and were added into four 250 mL volumetric flasks, then 250 mL DMF was added into the flasks respectively, to prepare DMF solutions with a concentration of 5 x 10 -5 mol / L, and were measured in a circular dichroism spectrometer (Applied Photophysics Chirascan). The signal intensity of compound 4a was the strongest in the circularly polarized luminescence spectrum, and the circularly polarized luminescence spectrum was shown in Figure 1 , wherein compound 4a showed a g lum value of 0.01 at 500 nm, and the luminescence asymmetry factor (g lum ) spectrum was shown in Figure 2

[0136] The above only describes the preferred embodiments of the present application, and it should be noted that, for those skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the protection scope of the present application.

Claims

1. A transcyclic chiral indazine compound of Formula I and its stereoisomers, characterized in that, The structure of the compound of formula I is as follows: R 1 Selected from acetyl Allyl Or benzoyl; R 2 Selected from H, C1-C6 alkyl or phenyl; R 3 Selected from H, C1-C6 alkyl or phenyl; R 4 Selected from R 5 Selected from phenyl, styryl, or naphthyl; Ar selected R is selected from H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl-C1-C6 alkoxy, C1-C6 alkylthio, halogen, TBSO-C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, amino, phenyl, naphthyl, or benzoynyl substituted with one or more halogens, C1-C6 alkyl, or halo-C1-C6 alkyl. n is a natural number between 0 and 3.

2. The compound according to claim 1, characterized in that, Selected from the following compounds:

3. The method for synthesizing the compound according to claim 1 or 2, characterized in that, Compound II was synthesized to give compound I in the presence of a catalyst and a chiral ligand, and the synthetic route is as follows: in, R 1 R 2 R 3 R 4 Ar is defined as in claim 1 or 2; The catalyst is selected from metal catalysts; The ligands are selected from chiral bioxazoline ligands and chiral phosphine ligands.

4. The method for synthesizing the compound according to claim 3, characterized in that, The catalyst is selected from copper catalysts; the ligand is selected from chiral bisarylphosphine ligands.

5. The method for synthesizing the compound according to claim 3, characterized in that, The catalyst is selected from tetrafluoroborate tetra(acetonitrile) copper catalyst as a metal catalyst; the ligand is selected from S-(-)-1,1′-binaphthyl-2,2′-bisdiphenylphosphine.

6. The synthesis method according to claim 3, characterized in that, Formula II: The molar ratio of catalyst to ligand is 1:0.03~0.1:0.036~0.

12.

7. The synthesis method according to claim 3, characterized in that, Formula II: The molar ratio of catalyst to ligand is 1:0.06:0.

072.

8. The method for synthesizing transcyclic chiral indazine compounds according to claim 3, characterized in that, The reaction temperature is -10℃ to 85℃.

9. The method for synthesizing transcyclic chiral indazine compounds according to claim 3, characterized in that, The reaction temperature is 0℃~30℃.

10. The method for synthesizing transcyclic chiral indazine compounds according to claim 3, characterized in that, The reaction temperature is 0℃~10℃.

11. The synthesis method according to claim 3, characterized in that, The reaction is carried out in a solvent, which is selected from halogenated hydrocarbon solvents.

12. The synthesis method according to claim 3, characterized in that, The reaction is carried out in a solvent, which is selected from dichloromethane or trichloromethane.

13. The synthesis method according to claim 3, characterized in that, The reaction is carried out in a solvent, which is selected from dichloromethane.

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