Boron-centered chiral boron dipyrromethene compounds and synthesis methods thereof

Abstract

The present invention belongs to the field of chiral boron compounds and discloses a boron-centered chiral boron dipyrromethene compound having a structure of general formula I or an enantiomer or diastereoisomer of general formula I: #imgabs0# wherein n is 0, 1, 2 or 3; R 1 is selected from phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, phenyl-substituted phenyl, halogen-substituted phenyl, thienyl, etc., wherein A is a benzene ring or a naphthalene ring, and R 2 is selected from hydrogen, alkyl, alkoxy, halogen, and R 3 is selected from phenyl, alkoxy-substituted phenyl, alkyl-substituted phenyl, hydroxy-substituted phenyl, trifluoromethyl-substituted phenyl, -NPh 2 Substituted phenyl, naphthyl, anthracene, etc. The present invention uses a Pd-catalyzed method to enantioselectively synthesize a boron-centered chiral boron dipyrromethene compound through an asymmetric intramolecular C-H arylation reaction. The compound has a novel skeleton and the product contains a six- to nine-membered boron heterocycle and a variety of substituents.

Description

Technical Field

[0001] The invention belongs to the field of chiral boron compounds, in particular to a boron-centered chiral boron dipyrromethene compound and a synthesis method thereof. Background Art

[0002] With the development of chiral colorimetric / fluorescent sensors and chiral responsive optoelectronics, the demand for chiral luminescent materials has gradually increased. Therefore, chemists continue to design new chiral organic dyes. Borondipyrromethene (BODIPYs) is a class of tetrasubstituted boron compounds. Due to their excellent optical properties and structural diversity, they have attracted much attention in recent decades and have been widely used in the fields of chemistry, biology, medicine and materials science. For example, they can be used as fluorescent sensors, biological labels and probes, laser dyes, photosensitizers, photodynamic therapy and optoelectronic devices.

[0003] Although a large number of structurally diverse boron dipyrromethene compounds have been reported in recent decades, few boron chiral boron dipyrromethene compounds or their synthesis methods have been reported. The known method is to use high performance liquid chromatography to resolve the racemate, and there are only two reports.

[0004] Therefore, the prior art lacks methods for constructing boron-centered chiral boron dipyrromethene compounds. Considering their importance and application value, it is necessary to explore and develop enantioselective synthesis methods to efficiently synthesize such compounds. Summary of the invention

[0005] The purpose of the present invention is to provide a class of novel boron-centered chiral boron dipyrromethene compounds.

[0006] Another object of the present invention is to provide a method for synthesizing the compounds.

[0007] In order to achieve one of the above purposes, the present invention adopts the following technical solution:

[0008] Boron-centered chiral boron dipyrromethene compounds having a structure of general formula I or an enantiomer or diastereomer of general formula I:

[0009]

[0010] Wherein, n is 0, 1, 2 or 3;

[0011] R 1 is selected from the group consisting of phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, hydroxy-substituted phenyl, cyano-substituted phenyl, phenyl-substituted phenyl, halogen-substituted phenyl, thienyl, furanyl, pyrrolyl, thiazolyl, imidazolyl, pyridinyl, pyranyl, pyrimidinyl, cycloalkyl,

[0012] A is a benzene ring or a naphthalene ring,

[0013] The R 2 is selected from hydrogen, alkyl, alkoxy, halogen,

[0014] The R 3 Selected from phenyl, alkoxy-substituted phenyl, alkyl-substituted phenyl, hydroxy-substituted phenyl, cyano-substituted phenyl, phenyl-substituted phenyl, halogen-substituted phenyl, trifluoromethyl-substituted phenyl, -NPh2-substituted phenyl, naphthyl, anthracenyl, phenanthryl, thienyl, furanyl, pyrrolyl, thiazolyl, imidazolyl, pyridyl, pyranyl, pyrimidinyl, N-ethylcarbazolyl, and alkylthio.

[0015] Furthermore, the R 1 Selected from phenyl, alkyl-substituted phenyl, phenyl-substituted phenyl, halogen-substituted phenyl, thienyl, and cycloalkyl.

[0016] Furthermore, the R 1 Selected from phenyl, (C1-C4) alkyl-substituted phenyl, phenyl-substituted phenyl, chlorophenyl, fluorophenyl, bromophenyl, thienyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0017] Furthermore, the R 1 Selected from phenyl, methyl-substituted phenyl, phenyl-substituted phenyl, chlorophenyl, fluorophenyl, thienyl, and cyclopropyl.

[0018] Furthermore, the R 1 Selected from phenyl, 4-methylphenyl, 4-phenylphenyl, 4-chlorophenyl, 4-fluorophenyl, 2-thienyl, cyclopropyl.

[0019] Furthermore, the A is a benzene ring or a naphthalene ring, and the R 2 Selected from hydrogen, (C1-C4) alkyl, (C1-C4) alkoxy, fluorine, chlorine, and bromine.

[0020] Furthermore, the A is a benzene ring or a naphthalene ring, and the R 2 Selected from hydrogen, methyl, methoxy, fluorine and chlorine.

[0021] Furthermore, the A is a benzene ring and the R 2 is selected from hydrogen, alkyl, alkoxy, halogen, or said A is a naphthalene ring and said R 2 For hydrogen.

[0022] Furthermore, the A is a benzene ring and the R 2 is selected from hydrogen, (C1-C4) alkyl, (C1-C4) alkoxy, fluorine, chlorine, bromine, or said A is a naphthalene ring and said R 2 For hydrogen.

[0023] Furthermore, the A is a benzene ring and the R 2 is selected from hydrogen, methyl, methoxy, fluorine, chlorine, or said A is a naphthalene ring and said R 2 For hydrogen.

[0024] Furthermore, the R 3 The group selected from phenyl, alkoxy-substituted phenyl, alkyl-substituted phenyl, halogen-substituted phenyl, trifluoromethyl-substituted phenyl, -NPh2-substituted phenyl, naphthyl, anthracenyl, thienyl, N-ethylcarbazolyl, and alkylthio.

[0025] Furthermore, the R 3 Selected from phenyl, (C1~C4) alkoxy substituted phenyl, (C1~C4) alkyl substituted phenyl, chlorophenyl, fluorophenyl, bromophenyl, trifluoromethyl substituted phenyl, -NPh2 substituted phenyl, naphthyl, anthracenyl, thienyl, N-ethylcarbazolyl, (C1~C4) alkylthio.

[0026] Furthermore, the R 3 Selected from phenyl, methoxy-substituted phenyl, methyl-substituted phenyl, fluorophenyl, trifluoromethyl-substituted phenyl, -NPh2-substituted phenyl, naphthyl, anthracenyl, thienyl, N-ethylcarbazolyl, MeS-.

[0027] Furthermore, the R 3 Selected from phenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4,6-trimethylphenyl, 4-fluoromethyl, 3-trifluoromethylphenyl, 4-NPh2-phenyl, 2-naphthyl, 9-anthryl, 2-thienyl, 2-N-ethylcarbazolyl, MeS-.

[0028] Furthermore, the n is 0 or 1.

[0029] The boron-centered chiral boron dipyrromethene compound is selected from the following compounds or their enantiomers and diastereomers:

[0030]

[0031] A method for synthesizing a boron-centered chiral boron dipyrromethene compound comprises the following steps: using a palladium catalyst and a ligand, compound 1 is reacted as follows:

[0032]

[0033] The palladium catalyst is selected from Pd(dba)2, Pd(OAc)2, Pd(PPh3)4, Pd(acac)2, [Pd(allyl)Cl]2;

[0034] The ligand is selected from the following compounds:

[0035]

[0036] The n, R 1 , A, R 2 , R 3 As defined above; in compound 1, Br is located at the ortho position (see the structure of the specific substrate) to facilitate ring formation with the α position of pyrrole.

[0037] Furthermore, the amount of the palladium catalyst is at least 2.5 mol%.

[0038] Furthermore, the amount of the ligand is at least 5 mol%.

[0039] Furthermore, PivOH and Cs2CO3 are added into the reaction.

[0040] Furthermore, the amount of PivOH is at least 40 mol%.

[0041] Furthermore, the amount of Cs2CO3 used is at least 150 mol%.

[0042] Furthermore, the reaction uses Et2O or toluene as solvent.

[0043] Furthermore, the reaction temperature is 70-140°C.

[0044] Furthermore, the reaction time is 3 to 24 hours.

[0045] The basis for the dosage of palladium catalyst, ligand, PivOH and Cs2CO3 is relative to the dosage of compound 1. For example, the dosage of palladium catalyst is written in the form of 2.5 mol%, which means that 0.025 mol of ligand is used for every 1 mol of compound 1; the dosage of catalyst is written in the form of 5 mol%, which means that 0.05 mol of catalyst is used for every 1 mol of compound 1; the dosage of PivOH is written in the form of 40 mol%, which means that 0.4 mol of PivOH is used for every 1 mol of compound 1; the dosage of Cs2CO3 is written in the form of 150 mol%, which means that 1.5 mol of Cs2CO3 is used for every 1 mol of compound 1.

[0046] As used herein, "alkyl" refers to a saturated aliphatic hydrocarbon group, which is a straight or branched chain group containing 1 to 20 carbon atoms, preferably an alkyl group containing 1 to 12 carbon atoms, and more preferably an alkyl group containing 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl.

[0047] As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic ring having typically 3 to 12 ring carbon atoms, preferably 3 to 8 ring carbon atoms. The ring may be saturated or have one or more carbon-carbon double bonds. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl.

[0048] As used herein, "alkoxy" refers to -O-(alkyl) and -O-(cycloalkyl), wherein alkyl and cycloalkyl are as defined herein, and non-limiting examples of alkoxy include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, 2-pentoxy, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Alkoxy groups typically have 1 to 7 carbon atoms connected by an oxygen bridge.

[0049] As used herein, "halogen" refers to fluorine, chlorine, bromine and iodine.

[0050] The halophenyl group used herein refers to a phenyl group substituted with a halogen, wherein the definition of halogen is as described herein, and the same applies to other "XX substituted phenyl groups". The substituents on the benzene ring may be monosubstituted or polysubstituted, and when there are two or more substituents, the types of the substituents may be the same or different.

[0051] As used herein, "phenyl" refers to

[0052] As used herein, "naphthyl" refers to Includes 1-naphthyl and 2-naphthyl.

[0053] As used herein, "hydroxy" refers to -OH.

[0054] As used herein, "cyano" refers to -CN.

[0055] As used herein, "thienyl" refers to Included are 1-thienyl and 2-thienyl.

[0056] As used herein, "alkylthio" refers to -O-(alkyl) wherein alkyl is as defined herein, and non-limiting examples of alkylthio include methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, pentylthio, 2-pentylthio, isopentylthio, neopentylthio, hexylthio, 2-hexylthio, and 3-hexylthio.

[0057] The presence of N-donors on the boron atom enhances the rigidity of tetracoordinated boron compounds and ensures the stability of the stereostructure, which provides an opportunity to construct a boron center. For the BODIPY structure, its core skeleton is composed of two pyrrole units connected by a carbon atom and a disubstituted boron atom. In the BODIPY molecule, the entire mother core is in a delocalized state, which can construct boron-centered chiral BODIPYs by desymmetrizing the bipyrrole. To achieve this goal, the remaining two substituent groups on the boron atom are crucial. The boron atom of common BODIPYs is replaced by two fluorine atoms, also known as F-BODIPYs. In recent years, N2O-BODIPYs have attracted the interest of researchers in many fields due to their good solubility, membrane permeability and structural diversity. More importantly, N2O-BODIPYs with π conjugation usually show light absorption and emission in the red to near-infrared (NIR) region, and can be used as near-infrared fluorescent probes because they can overcome interference from biological entities, such as biological absorption, light scattering and autofluorescence. The present invention uses N2O-BODIPY as a prochiral compound and produces π-conjugated N2O-BODIPY through an enantioselective intramolecular CH arylation reaction. The key to the reaction is to find an effective chiral metal catalyst and obtain an appropriate catalytic chiral pocket to accurately distinguish the two CH bonds of the dipyrrole skeleton of BODIPY, thereby achieving enantioselective CH functionalization and constructing boron-centered chiral BODIPYs.

[0058] The present invention has the following beneficial effects:

[0059] The present invention uses a Pd-catalyzed method to enantioselectively synthesize a boron-centered chiral boron dipyrromethene compound through an asymmetric intramolecular CH arylation reaction. The compound has a novel skeleton and the product contains a six- to nine-membered boron heterocycle and a variety of substituents. The key to the reaction is to use a Pd / TADDOL Phos catalytic system so that the two CH bonds of the dipyrrole can be accurately distinguished. The enantioselectivity of the reaction is excellent and the yield is good. The present invention also studies the photophysical properties of the compound and its application in chiral recognition. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 is the CD spectra of compounds 2a, 2w, 2aa, 2ac and their enantiomers from Example 32;

[0061] Figure 2 is the fluorescence spectrum of the reaction of compound (R)-3 of Example 38;

[0062] Figure 3 This is the fluorescence spectrum of the reaction of compound (S)-3 in Example 38. DETAILED DESCRIPTION

[0063] Conventional reactions were carried out under magnetic stirring and argon protection; catalytic reactions were carried out in an argon atmosphere and a colorless 5 mL microwave reaction tube. Anhydrous solvents (Et2O, CH2Cl2 and toluene) were obtained using an Inert Pure Solv solvent purification system. Thin layer chromatography (TLC) used Huanghai HSGF254 silica gel plates; TLC was developed using ultraviolet light (254, 365 nm). Silica gel column chromatography purification used GENERAR-REAGENT silica gel (200-300 mesh). Unless otherwise stated, all reagents were purchased from commercial suppliers (Adamas-beta, Bide Pharmatech, Energy Chemical, TCI, Aldrich, Alfa and J&K) and used directly without further purification. Nuclear magnetic resonance (NMR) spectra were recorded at ambient temperature using a Bruker DPX 400 or Bruker DPX 600 instrument. 1 H NMR is 400MHz or 600MHz, 13 C NMR is 101MHz or 151MHz, 19 F NMR is 376MHz or 565MHz, 11 B NMR is 128MHz or 193MHz. NMR standards are as follows: ( 1 H NMR) TMS = 0 ppm; ( 13 C NMR) CDCl3 = 77.16 ppm. The unit of chemical shift (δ) is ppm, and the unit of coupling constant (J) is Hertz (Hz). 1 H NMR data are reported as follows: chemical shift (δ, ppm), s indicates singlet, d indicates doublet, t indicates triplet, q indicates quartet, m indicates multiplet, and dd indicates doublet of doublets. 13 C NMR data are recorded in the form of chemical shift (δ, ppm). HPLC analysis was performed using Agilent 1260InfinityII, and chiral columns AD-3, IC, and AD-H were purchased from Daicel. High-resolution mass spectra (HRMS) were recorded using Agilent Technologies 6230TOF LC / MS under electrospray ionization (ESI) conditions. X-ray crystallography data were recorded using Bruker D8 VENTURE. Absorption spectra were measured using a UV-visible spectrophotometer (Shimadzu, UV3600). Emission spectra were measured using a Shimadzu RF-6000 spectrometer. Circular dichroism (CD) spectra were measured using an APPLIED PHOTOPHYSICS Chirascan CD spectrometer. Absolute fluorescence quantum yields were determined using an Edinburgh FLS 1000.

[0064] Example 1

[0065] Substrate synthesis

[0066]

[0067] Reference [Wang Z, et al. Organotrifluoroborate Salts as Complexation Reagents for Synthesizing BODIPY Dyes Containing Both Fluoride and an Organo Substituent at the Boron Center. J. Org. Chem., 84, 2732-2740 (2019)] Preparation. At room temperature, a mixture of S1 (1.0 mmol) and trimethylsilyl trifluoromethanesulfonate (0.18 mL, 1.0 mmol) in CH2Cl2 (14 mL) was stirred for 5 minutes. Then, a CH2Cl2 (14 mL) solution of S2 (5.0 mmol) and N, N-diisopropylethylamine (0.87 mL, 5.0 mmol) was added to the reaction. After stirring for 30 minutes, the mixture was diluted with water, washed with saturated Na2CO3 aqueous solution and brine, and dried over anhydrous Na2SO4. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography to obtain compound 1.

[0068]

[0069] Compound 1a, 90% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.75–7.71(m,4H),7.60–7.52(m,5H),7.44(dd,J=7.6,1.6Hz,1H),7.34–7.30(m,2H),7.28–7.26(m,1H) ,6.91(dd,J=4.2,1.0Hz,2H),6.86–6.81(m,1H),6.63–6.59(m,1H),6.44(dd,J=4.2,1.8Hz,2H),6.02(dd,J=8.2,1.4Hz,1H); 13 C NMR (151MHz, CDCl3) δ154.8,147.4,146.2,134.8,134.4,133.0,131.8,130 .7,130.6,130.3,128.5,128.0,127.7,127.2,121.0,119.0,118.7,116.6; 11B NMR (193MHz, CDCl3) δ1.72; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 27 H 21 BBrN2O] + :479.0925; measured value:479.0922.

[0070] Compound 1b, 70% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.71–7.70(m,2H),7.64–7.52(m,7H),7.43(dd,J=8.0,1.6Hz,1H),7.14(d,J=7.6Hz,2H),6.90(dd,J=4 .4,1.2Hz,2H),6.85–6.81(m,1H),6.63–6.58(m,1H),6.43(dd,J=4.2,1.8Hz,2H),6.02(dd,J=8.2,1.4Hz,1H),2.34(s,3H); 13 C NMR (151MHz, CDCl3) δ154.9,147.3,146.1,136.5,134.8,134.4,133.0,131.8 ,130.7,130.6,130.3,128.5,128.4,128.0,120.9,119.1,118.7,116.7,21.5; 11 B NMR (193MHz, CDCl3) δ1.75; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO] + :515.0901; measured value:515.0896.

[0071] Compound 1c, 79% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ7.81(d,J=7.6Hz,2H),7.74(s,2H),7.62–7.52(m,9H),7.46–7.39(m,3H),7.32–7.26(m, 1H),6.93(d,J=4.0Hz,2H),6.86–6.82(m,1H),6.62(t,J=7.4Hz,1H),6.46–6.44(m,2H),6.04(d,J=8.0Hz,1H); 13C NMR (151MHz, CDCl3) δ154.8,147.4,146.2,141.9,139.8,134.8,134.3,133.0,132.3,130 .7,130.6,130.4,128.8,128.5,128.0,127.2,126.9,126.4,121.0,119.0,118.8,116.6; 11 B NMR (193MHz, CDCl3) δ2.08; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 33 H 25 BBrN2O] + :555.1238; measured value:555.1233.

[0072] Compound 1d, 80% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.68–7.66(m,5H),7.61–7.53(m,5H),7.44(dd,J=7.6,1.6Hz,1H),7.29–7.27(m,2H),6.92(dd ,J=4.2,1.0Hz,2H),6.86–6.81(m,1H),6.64–6.60(m,1H),6.45(dd,J=4.2,1.9Hz,1H),6.00(dd,J=8.2,1.4Hz,1H); 13 C NMR (151MHz, CDCl3) δ154.6,147.5,146.1,134.8,134.2,133.3,133.1,133 .0,130.8,130.6,130.6,128.6,128.0,127.8,121.2,119.0,118.8,116.6; 11 BNMR (193MHz, CDCl3) δ1.42; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 27 H 20 BBrClN2O] + :513.0535; measured value:513.0539.

[0073] Compound 1e, 64% yield, as a red foam. 1H NMR (600MHz, CDCl3) δ7.76–7.67(m,4H),7.59–7.54(m,5H),7.44–7.43(m,1H),7.00(t,J =7.8Hz,2H),6.92(s,2H),6.83(m,1H),6.61(m,1H),6.44(s,2H),6.00(d,J=7.2Hz,1H); 13 C NMR(151MHz,CDCl3)δ162.7(d,J C-F =243.1Hz),154.7,147.5,146.1,134.8,134.2,133.5(d,J C-F =7.0Hz),133.0,130.8,130.5,130.5,128.66,128.0,121.1,119.0,118.8,116.6,114.4(d,J=19.6Hz); 11 B NMR (193MHz, CDCl3) δ1.47; 19 F NMR (565MHz, CDCl3) δ-116.19; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 19 BBrFN2NaO] + :519.0650; measured value:519.0648.

[0074]

[0075] Compound 1f, 56% yield, as a red foam. 1 H NMR(600MHz, CDCl3)δ7.76(s,2H),7.61–7.53(m,6H),7.42(d,J=7.8Hz,1H),7.27–7.26(m,2H) ,6.90(s,2H),6.83(t,J=7.5Hz,1H),6.60(t,J=7.5Hz,1H),6.44(s,2H),6.01(d,J=8.4Hz,1H); 13 C NMR (151MHz, CDCl3) δ154.7,147.3,146.2,134.6,134.3,132.9,131.3,130 .7,130.5,130.5,128.5,128.0,127.8,124.8,121.1,119.2,118.6,116.7; 11B NMR (193MHz, CDCl3) δ0.67; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 25 H 18 BBrN2NaOS] + :507.0308; measured value:507.0304.

[0076] Compound 1 g, 77% yield, in the form of red foam. 1 H NMR (400MHz, CDCl3) δ7.99(t,J=1.2Hz,2H),7.59–7.50(m,5H),7.36(dd,J=7.8,1.8Hz,1H),6.89(dd,J=4.4,1.2Hz,2H),6.78–6.73(m,1H),6.55– 6.51(m,1H),6.49(dd,J=4.2,1.8Hz,2H),5.84(dd,J=8.1,1.4Hz,1H),0. 84–0.82(td,J=4.6,2.7Hz,2H),0.51–0.47(m,2H),-0.06–-0.14(m,1H); 13 C NMR (101MHz, CDCl3) δ154.7,146.9,145.0,134.5,134.5,132.9,130.5,129.9,128.4,127.9,120.4,118.6,118.3,116.2,2.1; 11 B NMR (128MHz, CDCl3) δ1.75; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 24 H 21 BBrN2O] + :443.0925; measured value:443.0926.

[0077] Compound 1h, 61% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ8.20(d,J=8.4Hz,1H),7.83–7.76(m,2H),7.76(s,2H),7.62–7.51(m,6H),7.50–7.46(m,1H),7 .38–7.33(m,3H),7.30–7.26(m,2H),6.91(dd,J=4.2,1.0Hz,2H),6.42(dd,J=4.2,1.8Hz,2H),6.32(d,J=9.2Hz,1H); 13C NMR (151MHz, CDCl3) δ153.2,147.4,146.3,134.7,134.3,133.6,131.9,130.7,130.6,130 .4,129.6,128.5,128.1,127.8,127.7,127.2,127.0,126.5,123.7,120.1,118.8,113.0; 11 B NMR (128MHz, CDCl3) δ1.98; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 22 BBrN2NaO] + :551.0901; measured value:551.0898.

[0078] Compound 1i, 83% yield, as a red foam. 1 H NMR (600MHz, CDCl3) δ7.74(d,J=7.2Hz,2H),7.70(s,2H),7.61–7.59(m,3H),7.54(t,J=7.2Hz,2H),7.31(t,J=7.5Hz,2H),7.26–7.2 5(m,1H),6.92(d,J=4.2Hz,2H),6.72(t,J=7.8Hz,1H),6.64(d,J=7.8Hz,1H),6.43–6.42(m,2H),5.88(d,J=8.4Hz,1H),2.37(s,3H); 13 C NMR (151MHz, CDCl3) δ154.8,147.3,146.0,139.3,134.8,134.4,131.7,130.7 ,130.6,130.2,128.5,127.6,127.1,126.9,121.9,119.3,118.7,115.7,23.9; 11 B NMR (193MHz, CDCl3) δ1.69; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO] + :515.0901; measured value:515.0895.

[0079] Compound 1j, 67% yield, as a red foam. 1H NMR (400MHz, CDCl3) δ7.82(d,J=7.2Hz,2H),7.63(s,2H),7.57–7.49(m,5H),7.34–7.26(m,3H),6.99(d,J=8. 0Hz,1H),6.80(d,J=4.4Hz,2H),6.62(t,J=8.0Hz,1H),6.53(d,J=8.0Hz,1H),6.36–6.34(m,2H),3.31(s,3H); 13 C NMR (101MHz, CDCl3) δ153.8,146.9,146.1,145.5,135.0,134.7,132.7,130.5 ,130.3,129.7,128.4,127.3,126.9,124.8,121.6,118.3,117.6,110.5,56.0; 11 B NMR (128MHz, CDCl3) δ1.94; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO2] + :531.0850; measured value:531.0850.

[0080]

[0081] Compound 1k, 69% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ7.77–7.75(m,2H),7.66(t,J=1.4Hz,2H),7.63–7.53(m,5H),7.36–7.28(m,4H),6.9 4(dd,J=4.2,1.0Hz,2H),6.60(dd,J=8.4,2.4Hz,1H),6.46(dd,J=4.2,1.8Hz,2H),5.97(d,J=2.4Hz,1H); 13 C NMR (151MHz, CDCl3) δ155.6,147.7,146.3,134.9,134.2,133.2,133.1,132 .0,130.7,130.7,130.5,128.6,127.7,127.3,121.0,119.5,118.9,114.7; 11 B NMR (128MHz, CDCl3) δ1.85; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 19BBrClN2NaO] + :535.0355; measured value:535.0352.

[0082] Compound 11, 73% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.73–7.72(m,2H),7.68(s,2H),7.62–7.53(m,5H),7.38–7.27(m,4H),6.94(d d,J=4.2,1.0Hz,2H),6.46(dd,J=4.2,1.8Hz,2H),6.40–6.35(m,1H),5.75(dd,J=11.6,2.8Hz,1H); 13 C NMR(151MHz,CDCl3)δ162.4(d,J C-F =244.6Hz),155.9(d,J C-F =10.6Hz),147.7,146.2,134.8,134.2,132.8(d,J C -F=10.6Hz),131.7,130.8,130.7,130.5,128.6,127.7,127.3,118.9,111.0,111.0,107.9(d,J C-F =22.7Hz),106.4(d,J C-F =24.2Hz); 11 B NMR (128 MHz, CDCl3) δ 1.77; 19 FNMR (376MHz, CDCl3) δ-113.67; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 19 BBrFN2NaO] + :519.0650; measured value:519.0648.

[0083] Compound 1m, 84% yield, as a red foam. 1H NMR (400MHz, CDCl3) δ7.74(d,J=6.8Hz,2H),7.70(s,2H),7.46–7.42(m,2H),7.32(t,J=6.8Hz,2H),7.27–7.26(m,1H),7.21–7.10 (m,3H),6.95(d,J=4.4Hz,2H),6.86–6.82(m,1H),6.63–6.59(m,1H),6.43(dd,J=4.2,1.8Hz,2H),6.03–6.01(m,1H),3.88(s,3H); 13 C NMR (101MHz, CDCl3) δ159.5,154.8,147.1,146.2,135.5,134.7,133.0,131.8,13 0.3,129.6,128.0,127.6,127.1,123.0,121.0,119.1,118.7,116.6,116.2,55.7; 11 B NMR (128MHz, CDCl3) δ1.68; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO2] + :531.0850; measured value:531.0844.

[0084] Compound 1n, 78% yield, as a red foam. 1 H NMR (600MHz, CDCl3) δ7.72(d,J=7.2Hz,2H),7.68(s,2H),7.57(d,J=8.4Hz,2H),7.44(d,J=7.8Hz,1H),7.31(t,J=7.2Hz,2H),7.25–7.24(m,1H),7. 06(d,J=8.4Hz,2H),6.95(d,J=4.2Hz,2H),6.81(t,J=7.8Hz,1H),6.60(t ,J=7.8Hz,1H),6.44(d,J=4.2Hz,2H),6.00(d,J=8.4Hz,1H),3.92(s,3H); 13 C NMR (151MHz, CDCl3) δ162.0,154.9,147.4,145.5,134.7,133.0,132.40,131.8 ,130.1,128.0,127.6,127.1,126.9,120.9,119.0,118.5,116.6,114.1,55.7; 11B NMR (193MHz, CDCl3) δ1.66; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO2] + :531.0850; measured value:531.0842.

[0085] Compound 1o, 68% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.72–7.70(m,2H),7.66(m,1H),7.49(d,J=8.8Hz,2H),7.43(dd,J=7.6,1.6Hz,1H),7.38–7.34(m,4H),7.30(t,J=7.0Hz,2H),7. 23–7.21(m,5H),7.18–7.12(m,4H),7.04(dd,J=4.0,0.8Hz,1H),6.81–6.77 (m,1H),6.60–6.55(m,1H),6.45–6.43(m,2H),5.99(dd,J=8.2,1.4Hz,1H); 13 CNMR(151MHz, CDCl3)δ154.9,150.9,147.4,146.8,145.0,134.5,132.9,132.3,131.7,12 9.9,129.8,128.0,127.6,127.0,126.9,126.0,124.7,120.8,120.6,118.9,118.3,116.6; 11 B NMR (128MHz, CDCl3) δ2.15; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 39 H 29 BBrN3NaO] + :668.1479; measured value:668.1473.

[0086]

[0087] Compound 1p, 85% yield, as a red foam. 1H NMR (400MHz, CDCl3) δ7.72–7.68(m,4H),7.47(dd,J=7.9,1.4Hz,1H),7.31(t,J=7.0Hz,2H),7.26–7.23(m,1H),6.99(d,J=5.2Hz,2H),6.81–6.77( m,1H),6.67(d,J=4.0Hz,2H),6.63–6.58(m,1H),6.36(dd,J=4.2,1.8Hz, 2H),6.15(dd,J=8.0,1.2Hz,1H),2.38(s,3H),2.21(s,3H),2.12(s,3H); 13 C NMR (101MHz, CDCl3) δ154.9,147.6,145.9,138.9,136.5,136.3,135.0,133.1,131.4,1 30.4,128.8,128.4,128.0,127.7,127.1,120.8,118.9,118.7,116.5,21.3,20.1,20.0; 11 B NMR (128MHz, CDCl3) δ1.78; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 30 H 26 BBrN2NaO] + :543.1214; measured value:543.1213.

[0088] Compound 1q, 72% yield, as a red foam. 1 H NMR (600MHz, CDCl3) δ7.72(d,J=7.2Hz,2H),7.68(s,2H),7.60(t,J=6.9Hz,3H),7.57–7.54(m,2H),7.36(dd,J=9.0,6.6Hz,1H),7.32(t, J=7.2Hz,2H),7.27(d,J=7.2Hz,1H),6.94(d,J=4.2Hz,2H),6.46(dd,J=3.9,1.5Hz,2H),6.39–6.36(m,1H),5.75(dd,J=11.1,2.7Hz,1H); 13 C NMR(151MHz,CDCl3)δ162.4(d,J C-F =244.6Hz),155.9(d,J C-F =10.6Hz),147.7,146.2,134.8,134.2,132.8(d,J C-F=10.6Hz),131.7,130.8,130.7,130.5,128.6,127.7,127.3,118.9,111.0(d,J C-F =4.5Hz),107.88(d,J C-F =22.7Hz),106.44(d,J C-F =24.2Hz); 11 B NMR (193MHz, CDCl3) δ1.67; 19 F NMR (565MHz, CDCl3) δ-113.68; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 19 BBrFN2NaO] + :519.0650; measured value:519.0649.

[0089] Compound 1r, 59% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.87–7.67(m,8H),7.44(dd,J=8.0,1.6Hz,1H),7.35–7.31(m,2H),7.29–7.25(m ,1H),6.88–6.82(m,3H),6.65–6.61(m,2H),6.47(dd,J=4.8,2.0Hz,1H),6.01(dd,J=8.2,1.4Hz,1H); 13 C NMR (101MHz, CDCl3) δ154.7,147.1,145.0,135.0,134.6,133.6,133.1,131.8,131.3(q,J C-F =33.3Hz),130.1,129.2,128.0,127.7,127.3,127.3,127.0(q,J C-F =8.1Hz),123.8(q,J C-F =274.7Hz),121.2,119.2,116.7; 11 B NMR (193 MHz, CDCl3) δ 1.74; 19 F NMR (376MHz, CDCl3) δ-62.61; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 19 BBrF3N2NaO] + :569.0618; measured value:569.0616.

[0090] Compound 1s, 64% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ8.09(s,1H),8.01–7.96(m,3H),7.77–7.73(m,4H),7.70–7.60(m,3H),7.46(dd,J=8.0,1.6Hz,1H),7.35–7.32(m,2H),7 .29–7.26(m,1H),6.95(dd,J=4.2,1.0Hz,2H),6.89–6.85(m,1H),6.65–6.61(m,1H),6.45(dd,J=4.4,2.0Hz,2H),6.08(dd,J=8.2,1.4Hz,1H); 13 C NMR (101MHz, CDCl3) δ154.9,147.4,146.1,134.9,134.2,133.0,132.7,131.8,131.8,130.7, 130.4,128.8,128.3,128.0,127.9,127.7,127.6,127.3,127.2,121.0,119.0,118.8,116.7; 11 B NMR (128MHz, CDCl3) δ1.86; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 22 BBrN2NaO] + :551.0901; measured value:551.0895.

[0091] Compound 1t, 70% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ8.62(s,1H),8.07(dd,J=8.4,4.4Hz,2H),7.92–7.86(m,3H),7.82(t,J=1.4Hz, 2H),7.56–7.41(m,7H),7.37–7.33(m,2H),7.08–7.04(m,1H),6.81–6.76(m,1H),6.34–6.30(m,5H); 13C NMR (101MHz, CDCl3) δ155.1,146.8,145.3,136.8,133.3,131.9,131.0,131.0,130.9,130.9,130.1,129.2,128 .6,128.5,128.3,127.9,127.3,127.1,127.0,126.8,126.2,126.0,125.7,125.6,121.5,119.8,119.1,117.0; 11 B NMR (128MHz, CDCl3) δ2.11; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 35 H 24 BBrN2NaO] + :601.1057; measured value:601.1056.

[0092]

[0093] Compound 1u, 64% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.74(dd,J=3.2,1.2Hz,1H),7.71–7.69(m,4H),7.55–7.53(m,1H),7.45–7.42(m,2H),7.32–7.28(m,2H),7.26–7. 24(m,1H),7.10(dd,J=4.0,1.2Hz,2H),6.83–6.79(m,1H),6.62–6.58(m,1H),6.45(dd,J=4.4,2.0Hz,2H),6.01(dd,J=8.2,1.4Hz,1H); 13 C NMR (101MHz, CDCl3) δ154.8,145.8,141.4,135.0,134.4,133.0,131.7,130 .0,129.8,129.7,128.0,127.6,127.1,126.8,120.9,118.9,118.6,116.6; 11 B NMR (128MHz, CDCl3) δ1.62; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 25 H 18 BBrN2NaOS] + :507.0308; measured value:507.0305.

[0094] Compound 1v, 56% yield, as a red foam.1 H NMR (400MHz, CDCl3) δ8.40–8.38(m,1H),8.18–8.14(m,1H),7.83–7.57(m,3 H),7.71(m,2H),7.58–7.46(m,4H),7.36–7.31(m,3H),7.28–7.27(m,1H),7 .03(dd,J=4.2,1.0Hz,2H),6.88–6.84(m,1H),6.64–6.60(m,1H),6.53–6.4 6(m,2H),6.09(dd,J=8.0,1.2Hz,1H),4.50–4.45(m,2H),1.55–1.51(m,3H); 13 CNMR(151MHz, CDCl3)δ155.0,148.9,144.9,141.6,140.7,135.0,133.0,131.7,130.6,128.8,128.0,127.6,1 27.0,126.9,125.2,123.6,123.2,122.8,121.0,120.8,120.1,119.0,118.4,116.6,109.2,108.5,38.1,14.1; 11 B NMR (193MHz, CDCl3) δ1.70; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 35 H 27 BBrN3NaO] + :618.1323; measured value:618.1330.

[0095] Compound 1w, 66% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.89–7.87(m,1H),7.68–7.64(m,4H),7.61–7.51(m,5H),7.41(dd,J=7.8,1.0Hz,1H),7.35–7.32(m,1H), 7.29–7.26(m,2H),7.24–7.19(m,1H),7.08–7.04(m,1H),6.93(dd,J=4.4,1.2Hz,2H),6.44(dd,J=4.4,2.0Hz,2H),4.31(s,2H); 13C NMR (151MHz, CDCl3) δ147.2,145.5,141.8,135.3,134.6,131.9,131.5,130.7 ,130.5,130.0,128.6,128.5,127.8,127.6,127.4,126.9,121.8,118.3,64.0; 11 B NMR (193MHz, CDCl3) δ2.46; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 22 BBrN2NaO] + :515.0901; measured value:515.0902.

[0096] Compound 1x, 63% yield, as a red foam. 1 H NMR(400MHz, CDCl3) δ7.88(d,J=7.2Hz,1H),7.66–7.63(m,4H),7.52–7.50(m,2H),7.41(dd,J=8.0,0.8Hz,1H),7.33(t,J=7.4Hz,1H),7.2 9–7.27(m,1H),7.25–7.21(m,2H),7.09–7.04(m,3H),6.97(dd,J=4.2,1.0Hz,2H),6.45(dd,J=4.2,1.9Hz,2H),4.29(s,2H),3.93(s,3H); 13 C NMR (151MHz, CDCl3) δ161.9,147.2,144.9,141.9,135.3,132.6,131.9,131.5,12 9.8,128.6,127.8,127.6,127.4,127.2,126.8,121.8,118.1,114.0,63.9,55.7; 11 B NMR (193MHz, CDCl3) δ2.62; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 29 H 24 BBrN2NaO2] + :545.1006; measured value:545.1000.

[0097] Compound 1y, 58% yield, as a red foam. 1H NMR(400MHz, CDCl3)δ7.96(d,J=7.2Hz,1H),7.60–7.56(m,4H),7.42(dd,J=8.0,1.2Hz,1H),7.36(t,J=7.4Hz,1H),7.31–7.28(m,2H),7.25–7.21(m ,1H),7.10–7.05(m,1H),6.99(s,2H),6.68(dd,J=4.4,1.2Hz,2H),6.37(d d,J=4.2,1.8Hz,2H),4.24(s,2H),2.38(s,3H),2.22(s,3H),2.20(s,3H); 13 C NMR (151MHz, CDCl3) δ147.4,145.5,141.8,138.7,136.5,136.3,135.7,131.9,131.6,130.7,1 28.5,128.4,128.3,128.2,127.8,127.6,127.4,126.9,121.6,118.4,63.9,21.3,20.3,20.0; 11 B NMR (193MHz, CDCl3) δ2.62; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 28 BBrN2NaO] + :557.1370; measured value:557.1370.

[0098]

[0099] Compound 1z, 70% yield, as a red foam. 1 H NMR(400MHz, CDCl3)δ8.18(s,1H),8.02–7.96(m,3H),7.90(d,J=7.2Hz,1H) ,7.77(dd,J=8.4,1.2Hz,1H),7.67(s,2H),7.64–7.61(m,2H),7.55(d,J=6.8 Hz,2H),7.43(d,J=7.6Hz,1H),7.37–7.27(m,3H),7.25–7.21(m,1H),7.09–7 .05(m,1H),6.97(d,J=4.0Hz,2H),6.46(dd,J=4.0,1.6Hz,2H),4.35(s,2H); 13C NMR (151MHz, CDCl3) δ147.2,145.4,141.8,135.5,134.2,132.8,132.1,131.9,131.5,130.8,13 0.1,128.8,128.7,128.2,128.0,127.8,127.8,127.6,127.4,127.2,126.9,121.8,118.4,64.0; 11 B NMR (193MHz, CDCl3) δ2.45; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 32 H 24 BBrN2NaO] + :565.1057; measured value:565.1056.

[0100] Compound 1aa, 77% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.63–7.61(m,2H),7.59–7.50(m,3H),7.45–7.43(m,3H),7.36–7.32(m,3H),7.25–7.16(m,4H ),7.05–7.01(m,1H),6.89(d,J=4.0Hz,2H),6.40(dd,J=4.2,1.8Hz,2H),3.42(t,J=7.0Hz,2H),2.99–2.96(m,2H); 13 C NMR (151MHz, CDCl3) δ146.9,145.3,139.7,135.2,134.7,132.7,132.0,131.2,13 0.7,130.4,129.7,128.4,127.7,127.5,127.2,126.6,124.9,118.2,61.7,39.4; 11 B NMR (193MHz, CDCl3) δ2.43; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 29 H 24 BBrN2NaO] + :529.1057; measured value:529.1052.

[0101] Compound 1ab, 80% yield, as a red foam. 1H NMR (400MHz, CDCl3) δ7.63–7.61(m,2H),7.58–7.49(m,3H),7.45–7.42(m,3H),7.32(dd,J=7.6,1.6Hz,1H),7.26–7.24(d,J=5.2Hz,2H),7.22–7. 19(m,1H),7.05–7.00(m,3H),6.88(dd,J=4.0,1.2Hz,2H),6.40(dd,J=4. 4,1.6Hz,2H),3.41(t,J=7.0Hz,2H),2.96(t,J=7.0Hz,2H),2.28(s,3H); 13 C NMR (151MHz, CDCl3) δ146.8,145.3,139.7,136.0,135.1,134.7,132.7,132.0,131. 3,130.7,130.4,129.6,128.4,128.3,127.7,127.2,124.9,118.2,61.7,39.4,21.4; 11 B NMR (193MHz, CDCl3) δ2.49; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 30 H 26 BBrN2NaO] + :543.1214; measured value:543.1205.

[0102] Compound 1ac, 74% yield, as a red foam. 1 H NMR (400MHz, CDCl3) δ7.69(s,2H),7.64–7.62(m,2H),7.57–7.44(m,6H),7.24–7.15(m,5H),7.02–6.98(m ,1H),6.91–6.90(m,2H),6.48–6.47(m,2H),3.21(t,J=6.4Hz,2H),2.84–2.80(m,2H),1.85–1.78(m,1H); 13 C NMR (151MHz, CDCl3) δ147.1,145.4,142.2,135.2,134.6,132.7,131.4,130.7,1 30.5,130.4,129.7,128.4,127.5,127.3,126.7,124.7,118.1,61.4,33.3,32.4; 11 B NMR (193MHz, CDCl3) δ2.35; HRMS (ESI, m / z) [M+Na]+ Accurate mass calculation [C 30 H 26 BBrN2NaO] + :543.1214; measured value:543.1212.

[0103] Example 2

[0104] The inventors selected N2O-BODIPY 1a containing a 2-bromophenoxy group connected to a boron atom as a substrate, added a Pd catalyst, screened a suitable phosphorus ligand, provided a catalytic pocket for the interaction of the N2O-BODIPY substrate, and accurately distinguished the two CH bonds of BODIPY. The use of ligands L1 to L3 had poor enantioselectivity, the use of ligand L4 had good yield and moderate enantioselectivity (82% yield, 73% ee), and the use of TADDOL ligand L5 with a more hindered 3,5-isopropyl-phenyl substitution further improved the yield and enantioselectivity (99% yield, 92% ee).

[0105]

[0106]

[0107]

[0108] Compound 2a, reaction time 12 hours, product 2a was purified by preparative TLC (petroleum ether / ethyl acetate=50:1), purple foam, 39.4 mg, 99% yield, 92% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=6.39 min, t(major)=7.86 min. 1 HNMR(600MHz, CDCl3)δ7.81(s,1H),7.66–7.65(m,2H),7.57–7.45(m,3H),7.46(dd,J=7.8,1.2Hz,1H),7.35–7.32(m,1H),7.22–7.17(m,3H) ,7.11–7.05(m,3H),6.99(d,J=4.2Hz,1H),6.89(d,J=3.6Hz,1H),6.84(t,J=7.2Hz,1H),6.77(d,J=4.2Hz,1H),6.45(dd,J=3.9,2.1Hz,1H); 13C NMR (151MHz, CDCl3) δ157.2,151.5,143.7,140.2,134.7,134.5,133.7,133.7,131.1,130 .7,130.5,130.5,128.6,127.5,127.2,126.8,126.6,120.2,119.8,118.4,117.0,116.1; 11 B NMR (193MHz, CDCl3) δ2.09; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 19 BN2NaO] + :421.1483; measured value:421.1489.

[0109] General synthesis method:

[0110]

[0111] In a glove box filled with argon, Pd(dba)2 (1.4 mg, 0.0025 mmol), L5 (4.6 mg, 0.005 mmol), PivOH (4.2 mg, 0.04 mmol), Cs2CO3 (49 mg, 0.15 mmol) and compound 1 (0.1 mmol) were added to a dry 5 mL microwave reaction tube, followed by Et2O or toluene (2.0 mL). The reaction tube was covered and taken out of the glove box, and the resulting mixture was placed in a preheated (70-140°C) aluminum block and stirred for 3-24 hours. The reaction mixture was then concentrated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (1:0-50:1) as the eluent to obtain the target product.

[0112] After obtaining the optimal reaction conditions, the inventors expanded the substrates. The expansion of substrates with different functional groups and skeletons showed that the method of the present invention can provide a variety of boron chiral BODIPYs. The introduction of substituents such as methyl (2b, 2i, 2p), phenyl (2c), chlorine (2d, 2k), fluorine (2e, 2l, 2q), methoxy (2j, 2m, 2n), amino (2o) and trifluoromethyl (2r) on the benzene ring, as well as naphthalene (2h, 2s), thiophene (2f, 2u), anthracene (2t), carbazole (2v) and cyclopropyl (2g) are all compatible in the reaction, and the desired BODIPYs products are obtained with moderate to good yields and excellent enantioselectivity. The phenoxy group is replaced by a benzyloxy group to obtain seven-membered ring BODIPYs products (2w-2z) with moderate yields and good enantioselectivity. In addition, eight-membered and nine-membered BODIPYs were also obtained, albeit in low yields, with good enantioselectivity (2aa–2ac).

[0113] Example 3

[0114]

[0115] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2b was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as purple foam, 40.8 mg, 99% yield, 92% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 5.85 min, t (major) = 8.39 min. 1 H NMR(600MHz, CDCl3)δ7.81(s,1H),7.65(d,J=7.2Hz,2H),7.56–7.55(m,1H),7.52(t,J =7.8Hz,1H),7.46(dd,J=7.8,1.2Hz,1H),7.35–7.32(m,1H),7.17(d,J=8.4Hz,1H),7.1 1(d,J=7.8Hz,2H),6.98(d,J=4.2Hz,1H),6.92(d,J=7.2Hz,2H),6.89(d,J=4.2Hz,1H), 6.84(t,J=7.2Hz,1H),6.77(d,J=4.8Hz,1H),6.45(dd,J=3.9,1.7Hz,1H),2.18(s,3H); 13C NMR (151MHz, CDCl3) δ157.2,151.4,143.7,140.2,136.2,134.7,134.5,133.7,131.1,13 0.8,130.5,130.4,128.6,128.4,127.2,126.6,120.2,119.8,118.4,116.9,116.0,21.4; 11 B NMR (193MHz, CDCl3) δ2.17; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO] + :435.1639; measured value:435.1640.

[0116] Example 4

[0117]

[0118] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2c was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as a red foam, 31.8 mg, 67% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 8.20 min, t (major) = 9.12 min. 1 H NMR (600MHz, CDCl3) δ7.86(s,1H),7.68(d,J=7.2Hz,2H),7.59–7.53(m,3H),7.50(d,J=7.2Hz,1H),7.47(d,J=7.8Hz,2H),7.38–7.32(m,5H),7.28(d ,J=7.8Hz,2H),7.24–7.20(m,2H),7.02(d,J=4.2Hz,1H),6.93(d,J=3.6Hz ,1H),6.87(t,J=7.5Hz,1H),6.81(d,J=4.8Hz,1H),6.49(d,J=1.8Hz,1H); 13C NMR (151MHz, CDCl3) δ157.2,151.5,143.8,141.8,140.3,139.5,134.8,134.5,133.8,133.7,131.2, 131.2,130.5,130.5,128.6,127.3,127.1,126.8,126.6,126.4,120.2,119.9,118.4,117.0,116.1; 11 B NMR (193MHz, CDCl3) δ2.48; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 33 H 23 BN2NaO] + :497.1796; measured value:497.1789.

[0119] Example 5

[0120]

[0121] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2d was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as a red foam, 30.7 mg, 71% yield, 86% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 5.99 min, t (major) = 8.83 min. 1 H NMR(600MHz, CDCl3)δ7.79(s,1H),7.66–7.65(m,2H),7.58–7.55(m,1H),7.54(t,J =7.2Hz,2H),7.48(dd,J=7.5,1.5Hz,1H),7.37–7.34(m,1H),7.17(d,J=7.8Hz,1H) ,7.13(d,J=7.8Hz,2H),7.06(d,J=7.8Hz,2H),7.02(d,J=4.5Hz,1H),6.91(d,J=4. 2Hz,1H),6.87(t,J=7.5Hz,1H),6.80(d,J=4.2Hz,1H),6.47(dd,J=3.9,2.1Hz,1H); 13C NMR (151MHz, CDCl3) δ156.9,151.4,143.9,140.1,134.6,134.3,133.9,133.6,132.6,132 .2,131.3,130.6,130.5,128.7,127.7,127.5,126.6,120.2,120.1,118.3,117.1,116.2; 11 BNMR (193MHz, CDCl3) δ1.82; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 18 BClN2NaO] + :455.1093; measured value:455.1092.

[0122] Example 6

[0123]

[0124] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2e was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as purple foam, 41.2 mg, 99% yield, 93% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 5.80 min, t (major) = 7.445 min. 1 H NMR (600MHz, CDCl3) δ7.79(s,1H),7.65(d,J=7.2Hz,2H),7.58–7.55(m,1H),7.52(t,J=7.2Hz,2H),7.47(dd,J=7.8,1.8Hz,1H),7.37–7.34(m ,1H),7.18–7.15(m,3H),7.00(d,J=4.2Hz,1H),6.90(d,J=3.6Hz,1H),6.86(t,J=7.2Hz,1H),6.79–6.76(m,3H),6.46(dd,J=4.2,1.8Hz,1H); 13C NMR (151MHz, CDCl3) δ162.32(d,J=244.6Hz),157.0,151.4,143.8,140.2,134.6,134.4,133.8,133.6,132.3(d,J=6 .0Hz),131.3,130.6,130.5,128.6,127.4,126.6,120.04(d,J=25.7Hz),118.3,117.0,116.1,114.31(d,J=18.1Hz); 11 B NMR (193MHz, CDCl3) δ1.19; 19 F NMR (376MHz, CDCl3) δ-116.41; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 18 BFN2NaO] + :439.1388; measured value:439.1382.

[0125] Example 7

[0126]

[0127] The reaction temperature was 80°C, the reaction time was 24 hours, and the product 2f was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as a red foam, 6.1 mg, 15% yield, 91% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 6.74 min, t (major) = 7.84 min. 1 H NMR (600MHz, CDCl3) δ7.84(s,1H),7.63(d,J=7.2Hz,2H),7.57–7.50(m,4H),7.36(t,J=7.8Hz,1H),7.16(d,J=8.4Hz ,1H),7.05–7.04(m,1H),6.95(dd,J=15.0,4.2Hz,3H),6.90(t,J=7.5Hz,1H),6.80–6.77(m,3H),6.51–6.50(m,1H); 13C NMR (151MHz, CDCl3) δ157.2,151.4,143.5,140.4,134.8,134.4,133.8,133.5,131 .3,130.5,128.6,127.2,126.6,126.4,124.6,120.1,119.9,118.3,116.9,116.1; 11 B NMR (193MHz, CDCl3) δ1.19; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 25 H 17 BN2NaOS] + :427.1047; measured value:427.1052.

[0128] Example 8

[0129]

[0130] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2 g was purified by preparative TLC (petroleum ether / ethyl acetate=50:1), which was a red foam, 30.8 mg, 85% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=4.81 min, t(minor)=5.05 min. 1 H NMR(400MHz, CDCl3)δ7.82(s,1H),7.60(dd,J=7.2,1.4Hz,1H),7.57–7.49(m,4H),7.34–7.30(m,1H),7.05(d,J=8.4Hz,1H),6.92 (d,J=4.4Hz,1H),6.88–6.84(m,2H),6.76(d,J=4.4Hz,1H),6.48(dd,J=4.4,2.0Hz,1H),0.16–0.12(m,2H),-0.08–-0.20(m,3H); 13 C NMR (101MHz, CDCl3) δ157.6,151.5,143.4,139.8,135.0,134.6,133.7,133.4,130. 7,130.4,130.3,128.5,126.7,126.2,120.0,119.4,118.4,116.2,115.5,1.7,0.8; 11 BNMR (128MHz, CDCl3) δ3.40; HRMS (ESI, m / z) [M+Na]+ Accurate mass calculation [C 24 H 19 BN2NaO] + :385.1483; measured value:385.1483.

[0131] Example 9

[0132]

[0133] The reaction temperature was 80°C, the reaction time was 12 hours, and the product was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) for 2 hours, as a red foam, 30.9 mg, 69% yield, 80% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 6.16 min, t (major) = 7.64 min. 1 H NMR (600MHz, CDCl3) δ8.20(d,J=8.4Hz,1H),7.86(d,J=9.0Hz,1H),7.79(s,1 H),7.76(d,J=7.8Hz,1H),7.71(d,J=7.2Hz,2H),7.58–7.54(m,3H),7.48(t,J =7.8Hz,1H),7.43(d,J=9.0Hz,1H),7.33(t,J=7.2Hz,1H),7.24(s,2H),7.18( d,J=4.2Hz,1H),7.08–7.04(m,4H),6.93(d,J=4.2Hz,1H),6.49–6.48(m,1H); 13 C NMR (151MHz, CDCl3) δ157.4,150.0,142.2,139.8,134.9,134.7,134.3,133.3,131.4,131.3,131.0, 130.7,130.4,129.1,129.0,128.6,127.7,127.5,126.8,126.3,124.3,123.8,121.9,119.7,116.9; 11 B NMR (193MHz, CDCl3) δ1.69; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 21 BN2NaO] + :471.1639; measured value:471.1635.

[0134] Example 10

[0135]

[0136] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2i was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as a red foam, 40.8 mg, 99% yield, 88% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 6.12 min, t (minor) = 6.39 min. 1 H NMR(600MHz, CDCl3)δ7.80(s,1H),7.67(d,J=7.8Hz,2H),7.59–7.52(m,3H),7.22(t,J=7.2Hz,3H),7.10–7.0 7(m,4H),6.99(d,J=3.6Hz,1H),6.91(d,J=3.0Hz,2H),6.67(d,J=7.8Hz,1H),6.46–6.45(m,1H),2.51(s,3H); 13 C NMR (151MHz, CDCl3) δ157.8,150.5,143.7,140.6,137.4,134.6,134.4,133.1,132.8,130.9 ,130.6,130.6,130.5,128.6,127.5,127.2,126.7,122.6,119.5,118.8,118.1,117.2,22.5; 11 B NMR (193MHz, CDCl3) δ1.64; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO] + :435.1639; measured value:435.1637.

[0137] Embodiment 11

[0138]

[0139] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2j was purified by preparative TLC (petroleum ether / ethyl acetate=30:1) as a red foam, 21.8 mg, 51% yield, 78% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=8.81 min, t(minor)=9.54 min. 1 H NMR (400MHz, CDCl3) δ7.90–7.89(m,1H),7.69–7.67(m,2H),7.58–7.51(m,3H),7.24(dd,J=7.8,1.4Hz,2H),7.12–7.06(m,4H),7.00(d ,J=4.8Hz,1H),6.96(dd,J=8.0,1.6Hz,1H),6.90(dd,J=4.2,1.0Hz,1H),6.82–6.77(m,2H),6.45(dd,J=4.0,2.0Hz,1H),3.98(s,3H); 13 C NMR (101MHz, CDCl3) δ151.3,150.8,147.2,143.8,141.1,134.7,134.5,133.6,130.9,130.7 ,130.6,130.5,128.6,127.5,127.4,126.8,119.5,119.0,118.6,117.0,116.2,115.8,56.7; 11 B NMR (128MHz, CDCl3) δ2.31; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO2] + :451.1588; measured value:451.1582.

[0140] Example 12

[0141]

[0142] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2k was purified by preparative TLC (petroleum ether / ethyl acetate=50:1) as a red foam, 31.1 mg, 72% yield, 91% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=4.60 min, t(minor)=7.11 min. 1 H NMR(600MHz, CDCl3)δ7.83(s,1H),7.67–7.66(m,2H),7.60–7.57(m,1H),7.54(t,J=7.5Hz,2H),7.39(d,J=7.8Hz,1H),7.19–7.18(m,3H),7.14– 7.09(m,3H),7.01(d,J=4.2Hz,1H),6.93(dd,J=3.9,0.9Hz,1H),6.84(dd,J=8.1,2.1Hz,1H),6.76(d,J=4.2Hz,1H),6.48(dd,J=3.9,2.1Hz,1H); 13 C NMR (151MHz, CDCl3) δ157.7,150.3,144.2,140.7,138.9,134.8,134.4,133.6,131.2,130 .7,130.6,130.5,128.7,127.8,127.6,127.2,127.0,120.4,120.3,117.3,117.2,115.8; 11 B NMR (193MHz, CDCl3) δ2.32; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 18 BClN2NaO] + :455.1093; measured value:455.1091.

[0143] Example 13

[0144]

[0145] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 21 was purified by preparative TLC (petroleum ether / ethyl acetate = 50:1) as a purple foam, 34.6 mg, 75% yield, 88% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 4.59 min, t (minor) = 5.88 min. 1 H NMR(400MHz, CDCl3)δ7.80(d,J=1.2Hz,1H),7.67–7.65(m,2H),7.58–7.53(m,3H),7.43(dd,J=8.6,6.6Hz,1H),7.21–7.19(m,2H),7.13 –7.08(m,3H),7.01(d,J=4.4Hz,1H),6.91–6.87(m,2H),6.73(d,J=4.8Hz,1H),6.58(td,J=8.4,2.4Hz,1H),6.46(dd,J=4.0,2.0Hz,1H); 13 C NMR (101MHz, CDCl3) δ166.5 (d, J = 252.5Hz), 159.1 (d, J = 14.1Hz), 150.8, 143.8, 140.1, 134.53 (d, J = 28.3Hz), 133.6, 131.4, 130.7 ,130.5,130.5,128.6,128.0(d,J=11.1Hz),127.6,127.3,127.0,117.0,115.8,115.2,107.8(d,J=22.2Hz),107.1(d,J=23.2Hz); 11 B NMR (128 MHz, CDCl3) δ 2.05; 19 F NMR (376MHz, CDCl3) δ-104.62; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 18 BFN2NaO] + :439.1388; measured value:439.1388.

[0146] Embodiment 14

[0147]

[0148] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2m was purified by preparative TLC (petroleum ether / ethyl acetate = 20:1) as a red foam, 15.8 mg, 37% yield, 92% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 7.10 min, t (major) = 7.38 min. 1 H NMR(400MHz, CDCl3)δ7.82(s,1H),7.49–7.42(m,2H),7.35(t,J=7.2Hz,1H),7.24–7.17(m,5H),7.12–7.07(m,4H),7.0 4(d,J=4.4Hz,1H),6.94(d,J=4.0Hz,1H),6.85(t,J=7.4Hz,1H),6.79(d,J=4.4Hz,1H),6.47–6.45(m,1H),3.88(s,3H); 13 C NMR (151MHz, CDCl3) δ159.6,157.2,151.6,143.5,140.3,135.7,134.6,133.8,133.7,131.2,13 0.8,129.7,127.5,127.2,126.8,126.6,123.1,120.2,119.8,118.4,116.9,116.1,116.1,55.6; 11 B NMR (193MHz, CDCl3) δ2.09; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO2] + :451.1588; measured value:451.1586.

[0149] Embodiment 15

[0150]

[0151] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2n was purified by preparative TLC (petroleum ether / ethyl acetate=20:1) as a red foam, 42.4 mg, 99% yield, 94% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=9.42 min, t(major)=9.83 min. 1H NMR(600MHz, CDCl3)δ7.81–7.80(m,1H),7.65–7.64(m,2H),7.48–7.46(m,1H),7.35–7.32(m,1H),7.20–7.18(m,3H),7.09–7.05(m,5H),7 .02(d,J=4.2Hz,1H),6.95(dd,J=3.9Hz,0.9Hz,1H),6.86–6.83(m,1H),6.78(d,J=4.2Hz,1H),6.47(dd,J=4.2Hz,1.8Hz,1H),3.91(s,3H); 13 C NMR (151MHz, CDCl3) δ161.9,157.1,150.8,143.8,139.9,134.7,133.6,133.5,132.3,131.0 ,130.7,127.5,127.1,127.0,126.7,126.5,120.1,119.8,118.5,116.8,115.8,114.2,55.7; 11 B NMR (193MHz, CDCl3) δ2.26; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO2] + :451.1588; measured value:451.1584.

[0152] Example 16

[0153]

[0154] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2o was purified by preparative TLC (petroleum ether / ethyl acetate = 20:1) as dark red foam, 56.0 mg, 99% yield, 93% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 7.24 min, t (major) = 9.62 min. 1H NMR (600MHz, CDCl3) δ7.79 (s, 1H), 7.56 (d, J = 8.4Hz, 2H), 7.47 (dd, J = 7.5, 1.5Hz, 1H), 7.35 (t, J = 8.1Hz, 5H), 7.21 (d, J = 7.8Hz, 4H),7.18–7.17(m,3H),7.16–7.13(m,4H),7.11–7.04(m,5H),6.85(t,J=7.2Hz,1H),6.79(d,J=4.8Hz,1H),6.48–6.47(m,1H); 13 C NMR (151MHz, CDCl3) δ157.0,150.6,150.3,146.9,143.9,139.6,134.5,133.4,133.4,132.1,130.9,130 .7,129.8,127.5,127.2,126.9,126.7,126.4,125.9,124.5,120.9,120.1,119.7,118.6,116.7,115.5; 11 B NMR (193MHz, CDCl3) δ2.37; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 39 H 28 BN3NaO] + :588.2218; measured value:588.2218.

[0155] Embodiment 17

[0156]

[0157] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2p was purified by preparative TLC (petroleum ether / ethyl acetate=30:1) as dark red foam, 33.5 mg, 76% yield, 91% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=3.85 min, t(major)=4.12 min. 1H NMR (600MHz, CDCl3) δ7.79 (s, 1H), 7.47 (d, J = 7.8Hz, 1H), 7.34 (t, J = 7.5Hz ,1H),7.26–7.24(m,3H),7.18(d,J=8.4Hz,1H),7.12–7.07(m,3H),6.97(d, J=13.2Hz,2H),6.85(t,J=7.2Hz,1H),6.79(d,J=3.0Hz,1H),6.72(d,J=3. 6Hz,1H),6.54(s,1H),6.36(s,1H),2.37(s,3H),2.26(s,3H),2.05(s,3H); 13 C NMR (151MHz, CDCl3) δ157.0,151.5,143.7,140.2,138.6,136.9,136.7,135.3,134.0,133.7,130.8,130. 3,129.7,128.3,128.3,127.5,126.8,126.6,126.0,120.2,119.9,118.5,116.9,115.8,21.3,20.4,20.0; 11 BNMR (193MHz, CDCl3) δ2.17; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 30 H 25 BN2NaO] + :463.1952; measured value:463.1947.

[0158] Embodiment 18

[0159]

[0160] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2q was purified by preparative TLC (petroleum ether / ethyl acetate=50:1) as a red foam, 21.2 mg, 51% yield, 92% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=6.86 min, t(major)=8.19 min. 1H NMR (600MHz, CDCl3) δ7.82(s,1H),7.66(dd,J=8.4,5.4Hz,2H),7.47(dd,J=7.7,1.5Hz,1H),7.37–7.33(m,1H),7.23(d,J=8.5Hz,2H),7.19(dd ,J=9.3,7.8Hz,3H),7.12–7.06(m,3H),6.97(d,J=4.5Hz,1H),6.86(dd,J=9.1,5.7Hz,2H),6.80(d,J=4.5Hz,1H),6.47(dd,J=4.0,1.9Hz,1H); 13 C NMR (151MHz, CDCl3) δ164.25 (d, J = 252.2Hz), 157.2, 151.7, 142.3, 140.4, 134.6, 133.9, 133.7, 132.4, 132.4, 130.9, 130 .7,130.51(d,J=3.0Hz),127.6,126.9(d,J=16.6Hz),126.6,120.2,119.9,118.3,117.1,116.3,115.90(d,J=22.65Hz); 11 B NMR (193 MHz, CDCl3) δ 2.20; 19 F NMR (565MHz, CDCl3) δ-109.65; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 27 H 18 BFN2NaO] + :439.1388; measured value:439.1383.

[0161] Embodiment 19

[0162]

[0163] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2r was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as a red foam, 29.8 mg, 64% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 99:1, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 5.45 min, t (minor) = 6.08 min. 1H NMR(400MHz, CDCl3)δ7.92(s,1H),7.84(d,J=7.2Hz,3H),7.67(t,J=7.8Hz,1H),7.48(dd,J=7.6,1.6Hz,1H),7.37–7.35(m,1H), 7.22–7.17(m,3H),7.14–7.07(m,3H),6.94(d,J=4.8Hz,1H),6.89–6.85(m,1H),6.83–6.80(m,2H),6.48(dd,J=4.0,2.0Hz,1H); 13 C NMR (151MHz, CDCl3) δ157.3,152.4,141.2,140.8,135.2,134.4,134.2,133.7,133.6,131.33(q,J=32.4Hz),130.8,130 .7,129.3,127.6,127.04(q,J=3.0Hz),127.0,126.8,126.8,123.9(q,J=273.3Hz),120.3,120.0,118.2,117.4,116.8; 11 B NMR (128 MHz, CDCl3) δ 2.19; 19 F NMR (376MHz, CDCl3) δ-62.56; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 18 BF3N2NaO] + :489.1356; measured value:489.1356.

[0164] Embodiment 20

[0165]

[0166] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2s was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as a red foam, 17.0 mg, 38% yield, 85% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 6.72 min, t (minor) = 7.94 min. 1H NMR (400MHz, CDCl3) δ8.18(s,1H),8.01–7.95(m,3H),7.85(s,1H),7.76(dd,J=8.4,1 .6Hz,1H),7.62–7.60(m,2H),7.49(dd,J=7.6,1.2Hz,1H),7.38–7.34(m,1H),7.26–7 .24(m,2H),7.20(d,J=8.0Hz,1H),7.15–7.08(m,3H),7.03(d,J=4.4Hz,1H),6.95–6. 94(m,1H),6.86(t,J=7.4Hz,1H),6.81(d,J=4.4Hz,1H),6.48(dd,J=4.2,1.8Hz,1H); 13 CNMR(101MHz, CDCl3)δ157.2,151.4,143.8,140.2,134.9,134.2,134.0,133.8,132.9,132.0,131.3,130.8 ,130.5,128.8,128.3,128.0,127.7,127.6,127.4,127.2,126.8,126.6,120.2,119.9,118.5,117.1,116.2; 11 B NMR (128MHz, CDCl3) δ2.15; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 21 BN2NaO] + :471.1639; measured value:471.1635.

[0167] Embodiment 21

[0168]

[0169] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2t was purified by preparative TLC (petroleum ether / ethyl acetate=40:1) as a red foam, 31.9 mg, 64% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=5.95 min, t(major)=7.56 min. 1H NMR (600MHz, CDCl3) δ8.61 (s, 1H), 8.06 (t, J = 7.5Hz, 2H), 8.02 (d, J = 9.0Hz, 1 H),7.90(s,1H),7.78(d,J=9.0Hz,1H),7.50–7.45(m,4H),7.41–7.34(m,5H), 7.22(d,J=6.0Hz,2H),7.19–7.16(m,1H),6.88(t,J=7.5Hz,1H),6.68(d,J=4. 8Hz, 1H), 6.49 (d, J = 4.2Hz, 1H), 6.30 (d, J = 1.8Hz, 1H), 6.24 (d, J = 3.6Hz, 1H); 13 C NMR (151MHz, CDCl3) δ157.3,151.9,141.3,140.3,137.0,135.9,134.0,131.1,131.1,131.0,130.8,130.6,128.9,128.5, 128.4,127.8,127.3,127.1,127.1,126.8,126.8,126.6,126.4,126.4,125.7,125.7,120.3,120.0,118.4,117.2,116.3; 11 B NMR (193MHz, CDCl3) δ2.47; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 35 H 23 BN2NaO] + :521.1796; measured value:521.1801.

[0170] Embodiment 22

[0171]

[0172] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2u was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as a red foam, 40.0 mg, 99% yield, 92% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (minor) = 8.37 min, t (major) = 9.29 min. 1H NMR(400MHz, CDCl3)δ7.81(s,1H),7.77(d,J=1.6Hz,1H),7.51–7.45(m,3H),7.34–7.32(m,1H),7.19–7.16(m,3H), 7.14(d,J=4.4Hz,1H),7.10–7.06(m,4H),6.85(t,J=7.4Hz,1H),6.79(d,J=4.4Hz,1H),6.47(dd,J=4.2,1.8Hz,1H); 13 C NMR (101MHz, CDCl3) δ157.1,151.2,140.0,137.8,135.2,134.3,133.7,133.4,130.8,130 .7,129.8,129.0,127.5,126.8,126.8,126.7,126.5,120.1,119.8,118.5,116.8,115.9; 11 B NMR (128MHz, CDCl3) δ2.05; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 25 H 17 BN2NaOS] + :427.1047; measured value:427.1045.

[0173] Embodiment 23

[0174]

[0175] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2v was purified by preparative TLC (petroleum ether / ethyl acetate=30:1) as a red foam, 18.0 mg, 35% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=11.32 min, t(minor)=12.58 min. 1H NMR (600MHz, CDCl3) δ8.45 (s, 1H), 8.17 (d, J = 7.8Hz, 1H), 7.84–7.82 (m, 2H ),7.56–7.49(m,4H),7.34–7.31(m,2H),7.25(s,2H),7.20(d,J=8.4Hz,1H ),7.12(t,J=7.2Hz,2H),7.09–7.05(m,3H),6.86(t,J=7.5Hz,1H),6.81(d ,J=4.2Hz,1H),6.50(s,1H),4.46(q,J=7.0Hz,2H),1.52(t,J=7.2Hz,3H); 13 C NMR (151MHz, CDCl3) δ157.1,150.3,145.5,141.5,140.7,139.6,135.1,133.9,133.3,131.5,130.8,128.7,127.6,127.5 ,126.7,126.4,125.3,123.4,123.3,122.9,121.0,120.1,119.9,119.7,118.7,116.8,115.7,109.1,108.6,38.0,14.1; 11 B NMR (193MHz, CDCl3) δ2.39; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 35 H 27 BN3O] + :516.2242; measured value:516.2250.

[0176] Embodiment 24

[0177]

[0178] The reaction temperature was 70°C, the reaction time was 5 hours, and the product 2w was purified by preparative TLC (petroleum ether / ethyl acetate=20:1) as a dark pink foam, 26.8 mg, 65% yield, 94% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=12.40 min, t(minor)=17.91 min. 1H NMR(400MHz, CDCl3)δ7.94(s,1H),7.76–7.74(m,1H),7.62–7.60(m,2H),7.58–7.47(m,4H),7.43–7.37(m,2H),7.04(d,J=4.4Hz,1H),6 .97–6.94(m,4H),6.82(d,J=4.4Hz,1H),6.69–6.67(m,2H),6.58(dd,J=4.0,1.6Hz,1H),4.94(d,J=12.0Hz,1H),4.78(d,J=12.0Hz,1H); 13 C NMR (101MHz, CDCl3) δ157.9,145.2,143.0,142.9,137.6,135.3,134.7,131.4,131.2,130.6 ,130.3,130.2,130.0,129.4,129.0,128.4,128.4,128.1,127.2,126.1,119.1,117.7,66.8; 11 B NMR (128MHz, CDCl3) δ3.48; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 28 H 21 BN2NaO] + :435.1639; measured value:435.1631.

[0179] Compound 2w was dissolved in chloroform and n-hexane to obtain single crystals for X-ray diffraction using Bruker D8 and CuKα radiation. The crystal structure was collected and deposited in the Cambridge Crystallographic Data Center (https: / / www.ccdc.cam.ac.uk / ) with the accession number CCDC 2175350. The detailed information is shown in the table below:

[0180]

[0181]

[0182] Embodiment 25

[0183]

[0184] The reaction temperature was 70°C, the reaction time was 5 hours, and the product 2x was purified by preparative TLC (petroleum ether / ethyl acetate=20:1) as a red foam, 27.0 mg, 61% yield, 83% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=17.72 min, t(minor)=24.96 min. 1 H NMR (400MHz, CDCl3) δ7.92–7.91(m,1H),7.75–7.73(m,1H),7.59–7.57(m,2H),7.49 –7.46(m,1H),7.42–7.36(m,2H),7.08(d,J=4.4Hz,1H),7.05–7.03(m,2H),7.00(dd, J=4.4,1.2Hz,1H),6.94–6.93(m,3H),6.82(d,J=4.4Hz,1H),6.68–6.66(m,2H),6.59 (dd,J=4.2,1.8Hz,1H),4.93(d,J=12.0Hz,1H),4.77(d,J=12.0Hz,1H),3.90(s,3H); 13 C NMR (101MHz, CDCl3) δ161.6,157.3,145.2,142.9,142.4,137.6,135.2,132.3,131.5,131.0 ,130.3,129.9,129.3,128.9,128.2,128.0,127.2,126.1,118.9,117.5,114.0,66.8,55.6; 11 B NMR (128MHz, CDCl3) δ3.42; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 29 H 23 BN2NaO2] + :465.1745; measured value:465.1744.

[0185] Embodiment 26

[0186]

[0187] The reaction temperature was 70°C, the reaction time was 5 hours, and the product 2y was purified by preparative TLC (petroleum ether / ethyl acetate=40:1) as a red foam, 27.3 mg, 60% yield, 88% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=8.23 min, t(minor)=11.32 min. 1 H NMR (600MHz, CDCl3) δ7.94(s,1H),7.77(d,J=8.4Hz,1H),7.49–7.48(m,1H),7.42–7.40(m,2H),6.96–6.92(m,5H),6.78–6.77(m,2H),6.72(d,J= 3.6Hz, 1H), 6.64 (d, J = 3.0Hz, 2H), 6.53 (d, J = 4.2Hz, 1H), 4.94 (d, J = 12. 0Hz,1H),4.80(d,J=12.2Hz,1H),2.36(s,3H),2.12(s,3H),1.93(s,3H); 13 C NMR (151MHz, CDCl3) δ157.8,145.3,143.0,142.8,138.5,138.0,137.1,136.3,135.7,131.4,130.7,130.5,1 30.0,129.8,129.4,128.9,128.3,128.1,128.1,127.2,127.1,126.1,119.0,117.7,66.9,21.3,20.1,20.0; 11 BNMR (193MHz, CDCl3) δ3.72; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 31 H 27 BN2NaO] + :477.2109; measured value:477.2108.

[0188] Embodiment 27

[0189]

[0190] The reaction temperature was 80°C, the reaction time was 12 hours, and the product 2z was purified by preparative TLC (petroleum ether / ethyl acetate=40:1) as a red foam, 13.9 mg, 30% yield, 83% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(major)=13.53 min, t(minor)=19.67 min. 1 H NMR(600MHz, CDCl3)δ8.11(s,1H),7.99–7.94(m,4H),7.89(d,J=8.4,1H),7.72(d, J=7.8Hz,1H),7.62–7.58(m,2H),7.50(d,J=7.2Hz,1H),7.44–7.39(m,2H),7.08(d ,J=4.2Hz,1H),7.00(d,J=3.6Hz,1H),6.98–6.97(m,3H),6.85(d,J=4.2Hz,1H),6. 72–6.71(m,2H),6.61–6.60(m,1H),4.97(d,J=12.0Hz,1H),4.81(d,J=12.6Hz,1H); 13 C NMR (151MHz, CDCl3) δ157.9,145.2,143.0,142.9,137.8,135.4,134.0,132.8,132.2,131.4,131.3,130.5,13 0.3,130.1,129.4,129.0,128.7,128.5,128.1,128.0,127.8,127.6,127.3,127.1,126.2,119.2,117.8,66.8; 11 B NMR (193MHz, CDCl3) δ3.63; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 32 H 23 BN2NaO] + :485.1796; measured value:485.1790.

[0191] Embodiment 28

[0192]

[0193] The reaction temperature was 140°C, the reaction time was 3 hours, and the product 2aa was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as pink foam, 11.1 mg, 26% yield, 90% ee. The ee value was determined by Daicel Chiralpak IC column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 9.93 min, t (minor) = 12.31 min. 1 H NMR (400MHz, CDCl3) δ7.86 (s, 1H), 7.60–7.49 (m, 5H), 7.43 (t, J = 7.6Hz, 2H), 7 .37–7.31(m,2H),6.99–6.97(m,4H),6.92(dd,J=4.0,1.2Hz,1H),6.66–6.64( m,2H),6.58(dd,J=4.1,1.8Hz,1H),6.47(d,J=4.4Hz,1H),4.29(dd,J=10.8,8 .0Hz,1H),4.01–3.94(m,1H),3.24–3.16(m,1H),2.71(dd,J=13.2,6.0Hz,1H); 13 C NMR (101MHz, CDCl3) δ159.7,146.1,142.0,138.9,137.6,135.6,134.9,134.8,131.8,130.6,13 0.3,130.1,130.0,129.7,128.5,128.4,128.1,127.2,126.4,126.1,121.4,117.5,60.8,36.2; 11 B NMR (128MHz, CDCl3) δ3.49; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 29 H 23 BN2NaO] + :449.1796; measured value:449.1794.

[0194] Embodiment 29

[0195]

[0196] The reaction temperature was 140°C, the reaction time was 3 hours, and the product 2ab was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as pink foam, 9.7 mg, 22% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 6.34 min, t (minor) = 22.96 min. 1 H NMR (600MHz, CDCl3) δ7.85 (s, 1H), 7.60–7.54 (m, 3H), 7.51 (t, J = 7.2Hz, 2H), 7.43 ( dd,J=14.1,7.5Hz,2H),7.36–7.31(m,2H),6.98(d,J=4.2Hz,1H),6.91(dd,J=4.2, 1.2Hz,1H),6.79(d,J=7.8Hz,2H),6.57–6.54(m,3H),6.46(d,J=4.2Hz,1H),4.28– 4.25(m,1H),3.98–3.93(m,1H),3.21–3.15(m,1H),2.72–2.68(m,1H),2.14(s,3H); 13 C NMR (151MHz, CDCl3) δ159.6,146.0,142.0,138.9,137.6,135.6,135.3,135.0,134.8,131.8,130. 7,130.7,130.6,130.2,130.0,129.7,128.5,128.3,128.1,126.4,121.3,117.4,60.7,36.2,21.3; 11 B NMR (193MHz, CDCl3) δ3.34; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 30 H 25 BN2NaO] + :463.1952; measured value:463.1943.

[0197] Embodiment 30

[0198]

[0199] The reaction temperature was 140°C, the reaction time was 24 hours, and the product 2ac was purified by preparative TLC (petroleum ether / ethyl acetate = 40:1) as an orange foam, 13.6 mg, 31% yield, 90% ee. The ee value was determined by Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 99:1, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 5.03 min, t (minor) = 6.19 min. 1 H NMR (400MHz, CDCl3) δ7.73–7.71(m,2H),7.62–7.55(m,3H),7.50(s,1H),7.35–7.32(m,2H),7.04(d,J=4.0Hz,1H),7.01–6.88(m,5H),6.61( d,J=6.8Hz,2H),6.46–6.41(m,3H),3.87(d,J=11.2Hz,1H),3.47(t,J=11.0Hz,1H),2.84–2.79(m,1H),2.34–2.16(m,2H),1.81–1.77(m,1H); 13 C NMR (151MHz, CDCl3) δ160.7,146.3,144.5,143.7,136.1,134.9,134.7,133.1,131.0,130.7,1 30.3,129.1,129.0,128.5,128.4,128.4,126.6,126.0,124.1,120.8,117.9,65.4,33.8,33.5; 11 B NMR (193MHz, CDCl3) δ2.62; HRMS (ESI, m / z) [M+Na] + Accurate mass calculation [C 30 H 25 BN2NaO] + :463.1952; measured value:463.1947.

[0200] Embodiment 31

[0201] Scale-up test

[0202]

[0203] In an argon-filled glove box, Pd(dba)2 (43.1 mg, 0.075 mmol), L5 (138.0 mg, 0.15 mmol), PivOH (122.5 mg, 0.12 mmol), Cs2CO3 (1.47 g, 4.5 mmol) and compound 1a (1.45 g, 3.0 mmol) were added to an oven-dried 250 mL pressure bottle, followed by Et2O (60 mL), the tube was capped and taken out of the glove box. The mixture was placed in a preheated (80 °C) aluminum block and stirred for 24 hours. The reaction mixture was then concentrated and purified by silica gel column chromatography using petroleum ether / ethyl acetate (50:1) as eluent to give the desired product 2a as a purple foam, 1.04 g, 87% yield, 92% ee.

[0204] Embodiment 32

[0205] The BODIPYs compounds of the present invention exhibit yellow to bright red fluorescence. Compared with substrate 1a (499nm, 546nm), the absorption and emission maxima (574nm, 614nm) of compound 2a have obvious red shifts, while compared with 2a, the absorption and emission maxima of 2w, 2aa, and 2ac have slight blue shifts. The quantum yield of substrate 1a is only 0.7%, and the quantum yield generally increases after ring formation, reaching 48.4% (compound 2aa).

[0206]

[0207] The absorption and emission spectra of compounds 1a, 2a, 2w, 2aa, and 2ac are -5 M was measured in CH3CN solution.

[0208] The chiral optical properties of compounds 2a, 2w, 2aa, 2ac and their enantiomers were further studied. -5 M CH3CN solution), and showed obvious Cotton effect at about 571, 535, 523 and 507 nm, respectively. Figure 1 The compound of the present invention has these characteristics and can be used in the field of luminescent materials.

[0209] To further study the application of the BODIPYs compounds of the present invention, the inventors derived 2a into several compounds with far-red / near-infrared (FR / NIR) emission. First, the tribromo compound 3 (90% yield, 92% ee) was prepared by direct bromination of 2a with NBS. The introduction of bromine atoms into BODIPY not only led to a significant red shift in absorption and emission (λ abs =609nm,λ em=646nm), and also provides multiple reaction sites for different conversions. N Ar reaction, compound 3 was reacted with amines and sulfide nucleophiles to introduce various functional groups at the α position of BODIDY, and the corresponding derivatives 4a-4d were obtained in high yields without affecting the ee value. Among them, the introduction of selenium atoms led to a 20nm red shift (up to 666nm).

[0210]

[0211]

[0212] The absorption and emission spectra of compounds 3, 4a, 4b, 4c, and 4d are -5 M was measured in CH3CN solution.

[0213] Embodiment 33

[0214]

[0215] 2a (199.1 mg, 0.5 mmol) and CH3CN (100 mL) were added to a 250 mL round-bottom flask equipped with a magnetic stirring bar. The reaction mixture was stirred at 0°C and NBS (275.9 mg, 1.55 mmol) was slowly added. After 2a was completely consumed at room temperature, the solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 100:1) to give compound 3 as a green-brown foam, 284.4 mg, 90% yield, 92% ee. The ee value was determined using a Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 99:1, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t (major) = 16.53 min, t (minor) = 21.60 min. 1 H NMR(600MHz, CDCl3)δ8.29(d,J=7.8Hz,1H),7.63–7.61(m,3H),7.58–7.56(m,2H),7.47(t,J=7.5Hz ,1H),7.33(d,J=8.3Hz,1H),7.24–7.23(m,2H),7.10–7.09(m,3H),7.06(s,1H),6.94–6.91(m,2H); 13C NMR (151MHz, CDCl3) δ156.9,147.0,141.1,134.8,133.0,132.4,132.3,132.1,131.2, 130.5,129.7,129.0,128.1,127.4,127.2,127.0,120.4,120.0,117.6,109.1,107.4; 11 B NMR (193MHz, CDCl3) δ2.45; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 27 H 17 BBr3N2O] + :632.8979; measured value:632.8978.

[0216] Embodiment 34

[0217]

[0218] Compound 3 (31.6 mg, 0.05 mmol), 4-methoxyaniline (9.2 mg, 0.075 mmol), Et3N (7.6 mg, 0.075 mmol) and CH3CN (2 mL) were added to a 10 mL round-bottom flask equipped with a magnetic stirring bar. The reaction mixture was stirred at room temperature under air for 0.5 hours. After the raw material 3 was completely consumed, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate=20:1) to obtain a blue foam compound 4a, 28 mg, 83% yield, 92% ee, and the ee value was determined using a Daicel Chiralpak AD-3 column (n-hexane / iPrOH=95:5, 1.0 mL / min), λ=365 nm, temperature=28°C, t(minor)=4.64 min, t(major)=5.95 min. 1 H NMR(400MHz, CDCl3)δ8.48(s,1H),8.30(dd,J=7.8,1.4Hz,1H),7.62–7.60(m,2H),7.53–7.50(m,3H),7.29–7.27(m,1H ),7.20–7.16(m,3H),7.11(s,1H),7.08–7.07(m,3H),6.95–6.91(m,3H),6.84–6.82(m,2H),6.76(s,1H),3.80(s,3H); 13C NMR (151MHz, CDCl3) δ158.9,154.8,154.7,136.3,135.5,134.6,134.1,131.7,131.3,130.7,130.4,130. 1,129.5,129.3,128.8,128.1,127.7,127.0,125.7,124.9,120.1,119.4,119.4,114.3,99.9,99.2,55.6; 11 B NMR (193MHz, CDCl3) δ2.15; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 34 H 25 BBr2N3O2] + :676.0401; measured value:676.0403.

[0219] Embodiment 35

[0220]

[0221] Compound 3 (31.6 mg, 0.05 mmol), 4-benzyloxyphenol (15 mg, 0.075 mmol), Cs2CO3 (48.8 mg, 0.15 mmol) and CH3CN (2 mL) were added to a 10 mL round-bottom flask equipped with a magnetic stirring bar. The mixture was stirred at room temperature for 0.5 h. After compound 3 was completely consumed, the solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20:1-10:1) to obtain 4b as a green-blue foam, 27.4 mg, 73% yield, 92% ee. The ee value was determined using a Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 99:1, 1.0 mL / min), λ = 365 nm, temperature = 28 ° C, t (major) = 15.31 min, t (minor) = 16.75 min. 1 H NMR(600MHz, CDCl3)δ8.22(d,J=7.8Hz,1H),7.66–7.65(m,2H),7.61–7.55(m,3H),7.42–7.36(m,4H),7.32(t,J=7.2Hz,2H),7.25(s,2H),7 .13(d,J=8.4Hz,1H),7.04(m,3H),6.99(d,J=5.4Hz,2H),6.86(t,J=7.2Hz,1H),6.80(d,J=7.8Hz,2H),6.65(d,J=7.8Hz,2H),5.01(s,2H); 13C NMR (151MHz, CDCl3) δ158.3,156.6,155.7,149.7,143.8,141.1,137.0,133.3,131.7,131.6,131.0,130.9,130.5,13 0.2,128.9,128.7,128.2,127.9,127.7,127.5,127.0,126.5,120.3,119.7,119.6,118.3,115.5,104.6,95.2,70.6; 11 B NMR (193MHz, CDCl3) δ1.86; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 40 H 28 BBr2N2O3] + :753.0554; measured value:753.0548.

[0222] Embodiment 36

[0223]

[0224] Compound 3 (31.6 mg, 0.05 mmol), 4-methoxythiophenol (10.5 mg, 0.075 mmol), Et3N (7.6 mg, 0.075 mmol) and CH3CN (2 mL) were added to a 10 mL round-bottom flask equipped with a magnetic stirring bar. The reaction mixture was stirred at room temperature for 0.5 hours. After compound 3 was completely consumed, the solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10:1) to obtain 4c as a green-blue foam, 31.1 mg, 90% yield, 90% ee. The ee value was determined using a Daicel Chiralpak AD-3 column (n-hexane / iPrOH = 95:5, 1.0 mL / min), λ = 365 nm, temperature = 28 ° C, t (minor) = 7.13 min, t (major) = 10.66 min. 1 H NMR (400MHz, CDCl3) δ7.70–7.68(m,2H),7.62–7.56(m,3H),7.52–7.43(m,2H),7.40–7.31(m,3H),7.12–7. 10(m,3H),7.05(d,J=4.4Hz,1H),6.95–6.93(m,3H),6.87(d,J=4.4Hz,1H),6.69–6.66(m,2H),3.75(s,3H); 13C NMR (151MHz, CDCl3) δ159.2,157.9,152.8,144.7,140.6,134.7,134.5,134.4,133.9,133.4,132.2,131.2, 130.6,130.5,128.8,127.9,127.4,126.8,126.7,124.9,120.5,119.9,117.9,117.6,114.4,111.1,55.4,; 11 B NMR (193MHz, CDCl3) δ2.59; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 34 H 24 BBr2N2O2S] + :693.0013; measured value:693.0010.

[0225] Embodiment 37

[0226]

[0227] Referring to the literature [Fron, E. et al. Synthesis and photophysical characterization of chalcogen substituted BODIPY dyes. New J. Chem. 33, 1490-1496 (2009)], under an argon atmosphere, a solution of diphenyl diselenide (16.7 mg, 0.053 mmol) in ethanol (0.7 ml) was added to a solution of sodium borohydride (4.5 mg, 0.12 mmol) in ethanol (0.17 mL), and the resulting solution became colorless. The colorless solution was transferred to a solution of compound 3 (31.6 mg, 0.05 mmol) in THF (1.7 ml). The reaction mixture was kept under argon for 12 hours. The resulting solution was extracted with dichloromethane (10 mL) and brine, and the organic phase was dried over Na2SO4. The solution was dried by rotary evaporation, and the residue was purified by silica gel column chromatography using petroleum ether / ethyl acetate = 10:1 as eluent to obtain 4d as a green-blue foam, 24 mg, 68% yield, 90% ee. The ee value was determined using a Daicel Chiralpak AD-H column (n-hexane / iPrOH = 98.5:1.5, 1.0 mL / min), λ = 365 nm, temperature = 28°C, t(minor) = 6.07 min, t(major) = 6.44 min. 1H NMR(600MHz, CDCl3)δ8.29(d,J=7.8Hz,1H),7.66–7.65(m,2H),7.61–7.55(m,3H),7.45 (t,J=7.5Hz,1H),7.32–7.31(m,3H),7.15–7.13(m,1H),7.06(m,6H),6.97–6.92(m,4H); 13 C NMR (151MHz, CDCl3) δ158.0,146.3,143.9,140.6,136.0,134.4,133.5,133.2,132.5,132.3,131.7, 131.0,130.5,130.5,129.0,128.9,127.6,127.4,127.0,126.9,120.4,119.8,117.8,114.3,107.0; 11 B NMR (193MHz, CDCl3) δ2.23; HRMS (ESI, m / z) [M+H] + Accurate mass calculation [C 33 H 22 BBr2N2OSe] + :710.9352; measured value:710.9347.

[0228] Embodiment 38

[0229] Fluorescence reaction of compound (R)-3 with a pair of diamine enantiomers (1R,2R)-5 and (1S,2S)-5.

[0230]

[0231] When (R)-3(1.0×10 -5 M,CH3CN) and (1R,2R)-5(1.0×10 -3 When treated with 5-M, the fluorescence signal at λ = 628 nm was greatly enhanced, while (1S, 2S)-5 resulted in a slight enhancement of fluorescence. R The intensity ratio of / I0 is 3.9, and the enantioselective fluorescence enhancement ratio (ef=(I R -I0) / (I S -I0)) is 1.84. Figure 2 As shown, Figure 2 The curves of -a from bottom to top are (R)-3(1 equivalent, 1.0×10 -5 M, CH3CN) with 1, 2, 5, 10, 25, 50, 100 equivalents of (1R, 2R)-5; Figure 2 The curves of -b from bottom to top are (R)-3(1 equivalent, 1.0×10-5 M, CH3CN) and 1, 2, 5, 10, 25, 50, 100 equivalents of (1S, 2S)-5; Figure 2 The curves of -c from bottom to top are (R)-3(1 equivalent, 1.0×10 -5 M, CH3CN), its fluorescence spectra with 100 equivalents of (1S, 2S)-5, and its fluorescence spectra with 100 equivalents of (1R, 2R)-5; Figure 2 -d is the fluorescence intensity ratio of (1R,2R)-5 and (1S,2S)-5 to compound (R)-3 at 628 nm (λ exc =480nm, slit = 2 / 2 nm).

[0232] The fluorescence reaction of (S)-3 with (1R, 2R)-5 and (1S, 2S)-5 further confirmed the chiral recognition phenomenon. -5 M, CH3CN) and (1S,2S)-5(1.0×10 -3 When treated with (1R,2R)-5, the fluorescence signal at λ=628nm was greatly enhanced, while (1R,2R)-5 resulted in a small increase in fluorescence. Figure 3 As shown, Figure 3 The curves of -a from bottom to top are (S)-3(1 equivalent, 1.0×10 -5 M, CH3CN) with 1, 2, 5, 10, 25, 50, 100 equivalents of (1R, 2R)-5; Figure 3 The curves of -b from bottom to top are (S)-3(1 equivalent, 1.0×10 -5 M, CH3CN) and 1, 2, 5, 10, 25, 50, 100 equivalents of (1S, 2S)-5; Figure 3 The curves of -c from bottom to top are (S)-3(1 equivalent, 1.0×10 -5 M, CH3CN), its fluorescence spectra with 100 equivalents of (1R, 2R)-5, and its fluorescence spectra with 100 equivalents of (1S, 2S)-5; Figure 3 -d is the fluorescence intensity ratio of (1S,2S)-5 and (1R,2R)-5 to compound (S)-3 at 628 nm (λ exc =480nm, slit = 2 / 2 nm).

[0233] The above experiments prove that the compound of the present invention can be used as a new type of chiral fluorescent probe or sensor to identify chiral molecules.

[0234] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A boron-centered chiral boron dipyrromethene compound, characterized in that: It has the structure of general formula I or the enantiomers and diastereomers of general formula I: Wherein, n is 0, 1, 2 or 3; The R 1 is selected from phenyl, 4-methylphenyl, 4-phenylphenyl, 4-chlorophenyl, 4-fluorophenyl, 2-thienyl, cyclopropyl, A is a benzene ring and R 2 is selected from hydrogen, methyl, methoxy, fluorine, chlorine, or said A is a naphthalene ring and said R 2 is hydrogen; The R 3 selected from phenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4,6-trimethylphenyl, 4-fluoromethyl, 3-trifluoromethylphenyl, 4-NPh2-phenyl, 2-naphthyl, 9-anthryl, 2-thienyl, 2-N-ethylcarbazolyl, MeS- 。 2. A boron-centered chiral boron dipyrromethene compound, characterized in that: It is selected from the following compounds or their enantiomers and diastereomers: 。 3. A method for synthesizing the boron-centered chiral boron dipyrromethene compound according to claim 1 or 2, characterized in that: The following steps are involved: Using palladium catalyst and ligand, compound 1 reacts as follows: The palladium catalyst is selected from Pd(dba)2, Pd(OAc)2, Pd(PPh3)4, Pd(acac)2, [Pd(allyl)Cl]2; The ligand is selected from the following compounds: Where n, R 1 , A, R 2 , R 3 As defined in claim 1 or 2; The reaction was added with PivOH and Cs2CO3.

4. The legal method according to claim 3, characterized in that: The amount of the palladium catalyst is at least 2.5 mol%; and / or the amount of the ligand is at least 5 mol%; and / or the amount of PivOH is at least 40 mol%; and / or the amount of Cs2CO3 is at least 150 mol%; and / or the reaction uses Et2O or toluene as solvent; and / or the reaction temperature is 70-140°C; and / or the reaction time is 3-24 h.

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