A method for preparing an organoborolate intermediate and its application
The synthesis of organoboroate intermediates via palladium-catalyzed Suzuki reaction solves the toxicity and complexity issues of Stille coupling reaction, enabling the synthesis of efficient and environmentally friendly organic solar cell acceptor materials suitable for large-scale production.
Patent Information
- Application Number
- CN202512047247.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-31
- Publication Date
- 2026-05-26
Smart Images
Figure CN122080035A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for synthesizing an organic borate ester intermediate and its application. Background Technology
[0002] Currently, in the synthesis of high-performance organic solar cell acceptors, such as the classic Y-series acceptors, namely the ADA'DA acceptor, the electron acceptor (A) unit benzothiadiazole (BT) derivative and the electron donor (D) unit thiophene-thiophene derivative are commonly synthesized using the highly toxic Stille coupling reaction. Although the Stille reaction has excellent reactivity and functional group tolerance, the organotin reagents used have several significant problems: first, high toxicity, harmful to the human nervous system and the ecological environment; second, complex post-processing, with residual tin in the product being difficult to completely remove; and third, the toxicity of byproducts, which are also organotin reagents and similarly highly toxic. This hinders the large-scale production of Y-series acceptor materials and limits the practical application of organic solar cells.
[0003] In contrast, the palladium-catalyzed Suzuki reaction has become a commonly used method for constructing sp2-sp2 CC bonds due to its mild reaction conditions, non-toxicity, and environmental friendliness. Its non-toxic and environmentally friendly characteristics also facilitate the large-scale preparation of Y-series acceptor materials, thereby promoting the practical application of organic solar cells. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the background art above, and to provide a method for synthesizing an organoboroate intermediate that is non-toxic, environmentally friendly and highly reactive, as well as its application.
[0005] The technical solution of this application is: a method for preparing an organoboroate intermediate for Suzuki coupling reaction, comprising: Under an inert atmosphere, compound A in solvent 1 (Solvent 1) was prepared at temperatures ranging from -30°C to -28°C. o C is stirred at low temperature and reacts with B (OR) under the action of a strong alkali. 3 )3 After stirring the reaction at room temperature, it is then acidified to generate intermediate compound B; Intermediate compound B reacts with R under the action of desiccant and solvent 2 (Solvent 2). 2 (OH) n The reaction at room temperature yields an organoborolate intermediate compound (II); its chemical reaction formula is shown below:
[0006] The molar ratio of compound A to the base is 1:1.0 to 1:1.5; preferably 1:1.2. Compounds A and B (OR) 3 The molar ratio of 3 is 1:1.5 to 1:3.0; preferably 1:2.0. Compounds B and R 2 (OH) n The molar ratio is 1:1.0 to 1:1.5; preferably 1:1.1. X 1 R is a hydrogen atom or a nitro group. 1 R is any one of the following: hydrogen atom, C1-C20 alkyl group (e.g., methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, or eicosyl), substituted or unsubstituted phenyl group, or substituted or unsubstituted thiophene group. 2 (OH) n (n = 1 or 2) is a monohydric alcohol or a dihydric alcohol; The desiccant is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate, silica gel, and anhydrous calcium chloride.
[0007] In one implementation, when n is 1, R 2 The alkyl group remaining after removing two hydroxyl groups from a C1-C10 diol; when n is 2, R 2 It is any one of the alkyl, substituted or unsubstituted benzyl groups remaining after the removal of the hydroxyl group from a monohydric alcohol in C1-C10.
[0008] When n is 1, the structural formula of compound (II) is as follows: ; When n is 2, the structural formula of compound (II) is as follows:
[0009] In one embodiment, the alkyl group remaining after removing two hydroxyl groups from the C1-C10 diols is ethylenediol, propylenediol, butyldiol, neopentyldiol, or pinacol, and the alkyl group remaining after removing hydroxyl groups from the C1-C10 monools is methyl, ethyl, propyl, or isopropyl.
[0010] In one embodiment, the strong base is n-butyllithium, diisopropylaminolithium, or sodium hydride, and the acid used for acidification is any one of acetic acid, oxalic acid, sulfuric acid, and hydrochloric acid, preferably hydrochloric acid.
[0011] Solvent 1 is n-hexane or tetrahydrofuran, preferably tetrahydrofuran; solvent 2 is n-hexane, tetrahydrofuran, petroleum ether, dichloromethane or ethyl acetate.
[0012] In one embodiment, the low-temperature stirring is performed at -30 to -28°C. o Stirring at temperature C, preferably -30°C.o C.
[0013] Based on the same inventive concept, an application of an organoborolate intermediate compound (II) obtained according to the preparation method described above in the preparation of DA'D units of Y-series receptors is also provided.
[0014] Based on the same inventive concept, a method for preparing the DA'D unit of a Y-series receptor is also provided, using an organoborolate intermediate for the Suzuki coupling reaction obtained by the preparation method described above as a reactant, comprising: Under an inert atmosphere, compound (II), BT derivative C, and a base are coupled together in the presence of a catalyst to generate a compound with structure (I); the chemical reaction formula is shown below:
[0015] Among them, X 2 It is a hydrogen atom or a nitro group, and when X 1 When X is a hydrogen atom, 2 For nitro, when X 1 When it is nitro, X 2 It is a hydrogen atom; The molar ratio of BT derivative C to compound (II) is 1:2 to 1:2.4; preferably 1:2.2. The molar ratio of BT derivative C to catalyst is 1:0.01 to 1:0.05, preferably 1:0.05; the catalyst is a palladium catalyst. The molar ratio of BT derivative C to base is 1:2.5 to 1:3.0, preferably 1:3.0.
[0016] In one embodiment, the base is any one of NaHCO3, KHCO3, Na2CO3, K2CO3, Cs2CO3, CH3COONa, CH3COOK, NaOH, KOH, K3PO4, triethylamine, or diisopropylethylamine.
[0017] In one embodiment, the palladium catalyst is any one of bis(triphenylphosphine)palladium dichloride, tetra(triphenylphosphine)palladium, palladium acetate, DPPFpalladium dichloride, and palladium chloride, preferably palladium acetate.
[0018] In one embodiment, solvent 3 is any one of a mixture of tetrahydrofuran, toluene, DMF or dioxane and water, preferably a mixture of tetrahydrofuran and water, wherein the volume ratio of tetrahydrofuran, toluene, DMF or dioxane and water in the mixture is 10:1 to 1:1, preferably 10:1.
[0019] In one embodiment, the compound (II), BT derivative C, and base are reacted with a catalyst at a temperature of 20°C. o C~120 o C, preferably 70 o C. The preferred inert atmosphere is argon.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: the preparation method of the organoboroate intermediate provided by the present invention is simple, low in cost, and does not require an ultra-low temperature of -78°C; the reaction temperature only needs to be controlled between -30°C and -28°C. o The low-temperature environment of C ensures a non-toxic and environmentally friendly reaction, and post-processing does not produce toxic byproducts, posing no harm to the environment or human health. This method is suitable for large-scale synthesis. The organoboronic ester intermediates obtained using this method exhibit high reactivity, and their coupling with BT derivatives to prepare the DA'D unit of Y-series receptors shows high yields across a temperature range from room temperature to reflux. This provides a non-toxic, green, and large-scale method for synthesizing the key DA'D unit of Y-series receptors. Attached Figure Description
[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0022] Figure 1 The 1H NMR spectrum of the organoboroester intermediate a3 prepared in Example 1 of this invention; Figure 2 The carbon NMR spectrum of the organoboroate intermediate a3 prepared in Example 1 of this invention; Figure 3 The 1H NMR spectrum of organoboroester intermediate b3 prepared in Example 2 of this invention; Figure 4 The carbon NMR spectrum of organoboroate intermediate b3 prepared in Example 2 of this invention; Figure 5 The 1H NMR spectrum of organoboroester intermediate c3 prepared in Example 3 of this invention; Figure 6 The carbon NMR spectrum of organoboroate intermediate c3 prepared in Example 3 of this invention; Figure 7 The 1H NMR spectrum of the DA'D unit a4 of the Suzuki conjugate Y-series receptor prepared in Example 4 of this invention; Figure 8The carbon NMR spectrum of the DA'D unit a4 of the Suzuki coupling product Y-series receptor prepared in Example 4 of this invention; Figure 9 The 1H NMR spectrum of the DA'D unit b4 of the Suzuki conjugate Y-series receptor prepared in Example 5 of this invention; Figure 10 The carbon NMR spectrum of the DA'D unit b4 of the Suzuki coupling product Y-series receptor prepared in Example 5 of this invention; Figure 11 The 1H NMR spectrum of the DA'D unit c4 of the Suzuki conjugate Y-series receptor prepared in Example 6 of this invention; Figure 12 The image shows the carbon NMR spectrum of the DA'D unit c4 of the Suzuki coupling product Y-series receptor prepared in Example 6 of this invention. Detailed Implementation
[0023] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.
[0024] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.
[0025] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.
[0026] Please see Figure 1-12 Examples 1-3 are specific examples of the synthesis of compound (II), and Examples 4-6 are specific examples of the synthesis of compound (I). Details are as follows: Example 1 Compound a1 reacts with trimethyl borate under strong alkali to form an organoborate, which is then acidified with hydrochloric acid and post-treated to give organoborate intermediate a2. Compound a2 undergoes esterification with neopentyl glycol under the action of a drying agent, and is then purified to give organoborate ester intermediate a3.
[0027] Under an argon atmosphere, compound a1 (5.0 g) and THF (50 mL) were added to a 100 mL three-necked flask. The mixture was cooled to -30 °C, and LDA (2 M, 10.2 mL) was added. The mixture was stirred at low temperature for 1 hour, and then B(OMe)3 (3.53 g) was added. The mixture was stirred at room temperature for 12 hours, and then dilute hydrochloric acid (1 M, 50 mL) was added. The mixture was stirred for another hour to stop the reaction. The mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain crude a2, a brown oily liquid. The crude compound a2 obtained above, petroleum ether (100 mL), and 50 g of anhydrous magnesium sulfate were added to a 500 mL single-necked flask. The mixture was stirred until homogeneous, then neopentyl glycol (1.95 g) was added. The reaction was stirred at room temperature for 1 hour to complete the reaction. The mixture was filtered, washed three times with petroleum ether, and purified by column chromatography to obtain 4.9 g of purple solid a3. The two-step yield of a1→a3 was 71.0%. NMR data for a3: 1 H NMR (600MHz, CDCl3) δ 7.72 (s, 1H), 7.07 (s, 1H), 3.79 (s, 4H), 2.75 (t, J = 7.7 Hz, 2H), 1.79 (p, J = 7.6 Hz, 2H), 1.38 – 1.27 (m, 16H), 1.05 (s, 6H), 0.93 (t, J= 7.0 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 145.30, 140.14, 134.94, 128.04,123.89, 72.46, 32.10, 32.00, 30.09, 29.74, 29.70, 29.65, 29.49, 29.47, 29.43,28.66, 22.77, 21.91, 14.21.
[0028] Example 2 The process of synthesizing b3 from b1 is similar to the process of synthesizing a3 from a1, except that some of the raw materials and solvents are replaced:
[0029] Under an argon atmosphere, compound b1 (4.5 g) and n-hexane (50 mL) were added to a 100 mL three-necked flask. The mixture was cooled to -30 °C, and LDA (2 M, 10.2 mL) was added. The mixture was stirred at low temperature for 1 hour, and then B(Oi-Pr)3 (6.4 g) was added. The mixture was stirred at room temperature for 12 hours, and then dilute hydrochloric acid (1 M, 50 mL) was added. The mixture was stirred for another hour to stop the reaction. The mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain crude b2, a brown oily liquid. The crude compound b2 obtained above, petroleum ether (100 mL), and 50 g of anhydrous sodium sulfate were added to a 500 mL single-necked flask. The mixture was stirred until homogeneous, then neopentyl glycol (2.2 g) was added. The reaction was stirred at room temperature for 1 hour to complete the reaction. The mixture was filtered, washed three times with petroleum ether, and purified by column chromatography to obtain a grayish-white solid b3, with a yield of 84.5%. NMR data for b3 are as follows: 1 H NMR (400 MHz, CDCl3) δ7.67 (s, 1H), 7.05 (s, 1H), 3.78 (s, 4H), 2.72 (t, J = 7.7 Hz, 2H), 1.75 (p,J = 7.6 Hz, 2H), 1.39 – 1.21 (m, 12H), 1.04 (s, 6H), 0.92 – 0.83 (m, 3H). 13 CNMR (151 MHz, CDCl3) δ 145.18, 140.01, 134.88, 127.90, 123.76, 72.37, 32.03,31.81, 29.96, 29.46, 29.34, 29.32, 29.24, 28.52, 22.61, 21.82, 14.05.
[0030] Example 3 The process of synthesizing c3 from c1 is similar to the process of synthesizing a3 from a1, except that some of the raw materials and solvents are replaced:
[0031] Under an argon atmosphere, compound c1 (5.5 g) and THF (50 mL) were added to a 100 mL three-necked flask. The mixture was cooled to -30 °C, and LDA (2 M, 10.2 mL) was added. The mixture was stirred at low temperature for 1 hour, and then B(OMe)3 (4.0 g) was added. The mixture was stirred at room temperature for 12 hours, and then dilute hydrochloric acid (1 M, 50 mL) was added. The mixture was stirred for another hour to stop the reaction. The mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain crude c2, a brown oily liquid. The crude compound C2 obtained above, 100 mL of n-hexane, and 50 g of anhydrous sodium sulfate were added to a 500 mL single-necked flask. The mixture was stirred until homogeneous, then neopentyl glycol (3.0 g) was added. The reaction was stirred at room temperature for 1 hour to complete the reaction. The mixture was filtered, washed three times with petroleum ether, and purified by column chromatography to obtain a brown, transparent, oily liquid, C3, with a yield of 78.6%. NMR data for C3 are as follows: 1 H NMR (500 MHz, CDCl3) δ 7.69 (s, 1H), 7.04 (s, 1H), 3.79 (s, 4H), 2.66 (d, J = 7.2 Hz, 2H), 1.90 (h, J = 5.1, 4.0 Hz, 1H), 1.33 – 1.23 (m, 16H), 1.05 (s, 6H), 0.89 (t, J= 7.0 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 145.56, 140.04, 134.12, 128.02,124.68, 72.47, 37.12, 35.02, 33.63, 33.33, 32.10, 31.90, 29.70, 28.82, 26.54,23.08, 22.69, 21.90, 14.15, 14.13.
[0032] Example 4 Compound (II) under palladium catalysis underwent Suzuki cross-coupling with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole, followed by purification to obtain the DA'D unit a4 of the Y-series receptor:
[0033] Under an argon atmosphere, compound a3 (463 mg), 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole (200 mg), and THF / H2O (v / v, 30 mL / 3 mL) were added to a 100 mL three-necked flask. Palladium acetate (6.7 mg) and potassium carbonate (215.6 mg) were then added sequentially, and the temperature was raised to 70°C. o C. After stirring for 2 hours, the reaction was stopped. Dichloromethane (100 mL) was added for dilution, followed by water (50 mL). The mixture was extracted with dichloromethane (100 mL × 3 times), washed with saturated brine, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain a reddish-black solid. Column chromatography was used to purify the solid to obtain a4 (310 mg), a red solid, with a yield of 73.5%. NMR data for a4: 1H NMR (500 MHz, CDCl3) δ 7.71 (s, 2H), 7.17 (s, 2H), 2.78 (t, J = 7.7Hz, 4H), 1.79 (p, J = 7.5 Hz, 4H), 1.32 – 1.19 (m, 32H), 0.88 (t, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 152.10, 144.15, 141.68, 138.97, 135.00, 129.96,125.06, 124.00, 121.31, 31.81, 29.73, 29.60, 29.55, 29.53, 29.47, 29.28,29.24, 28.47, 22.58, 14.01.
[0034] Example 5 The process of synthesizing b4 from b3 is similar to that of synthesizing a4 from a3, only requiring the replacement of some reactants and solvents:
[0035] Under an argon atmosphere, compound b3 (431 mg), 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole (200 mg), and THF / H2O (v / v, 20 mL / 2 mL) were added to a 100 mL three-necked flask. Then, tetraphenylphosphine palladium (35 mg) and potassium carbonate (215.6 mg) were added sequentially, and the temperature was raised to 70°C. o C. After stirring for 2 hours, the reaction was stopped. Dichloromethane (100 mL) was added for dilution, followed by water (50 mL). The mixture was extracted with dichloromethane (100 mL × 3 times), washed with saturated brine, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain a reddish-black solid. Column chromatography was used to purify the solid to obtain red solid B4 (290.7 mg), with a yield of 74.04%. NMR data for B4 are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.71 (s, 2H), 7.18 (s, 2H), 2.78 (t, J =7.7 Hz, 4H), 1.79 (p, J = 7.6 Hz, 4H), 1.32 – 1.24 (m, 24H), 0.88 (t, J = 6.8Hz, 6H). 3C NMR (151 MHz, CDCl3) δ 152.21, 144.26, 141.79, 139.08, 135.11,130.06, 125.18, 124.10, 121.44, 31.90, 29.84, 29.71, 29.53, 29.39, 29.32,28.58, 22.69, 14.13.
[0036] Example 6 The process of synthesizing C4 from C3 is similar to that of synthesizing A4 from A3, only requiring the replacement of some reactants and solvents:
[0037] Under an argon atmosphere, compound C3 (480 mg), 4,7-dibromo-5,6-dinitrobenzo[C][1,2,5]thiadiazole (205 mg), and THF / H2O (v / v, 40 mL / 4 mL) were added to a 100 mL three-necked flask. Then, bis(triphenylphosphine)palladium dichloride (21 mg) and potassium carbonate (215.6 mg) were added sequentially, and the temperature was raised to 70°C. o C. After stirring for 2 hours, the reaction was stopped. Dichloromethane (100 mL) was added for dilution, followed by water (50 mL). The mixture was extracted with dichloromethane (100 mL × 3 times), washed with saturated brine, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure to obtain a reddish-black solid. Column chromatography was used to purify the solid to obtain red solid C4 (297 mg), yield 68.1%. NMR data for C4: 1 H NMR (500 MHz, CDCl3) δ 7.71 (s, 2H), 7.15 (s, 2H), 2.71 (d, J =7.0 Hz, 4H), 1.88 (q, J = 6.2 Hz, 2H), 1.34 – 1.26 (m, 32H), 0.89 (dd, J =8.9, 6.7 Hz, 12H). 13 C NMR (126 MHz, CDCl3) δ 152.21, 144.62, 141.78, 139.00,134.24, 130.08, 125.95, 124.07, 121.42, 37.30, 34.69, 33.56, 33.27, 31.89,29.64, 28.79, 26.53, 23.04, 22.69, 14.15, 14.14.
[0038] The above are merely preferred embodiments of the present invention. It should be noted that the present invention is not limited to the above embodiments. For those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should also be considered within the scope of protection of the present invention.
Claims
1. A process for the preparation of an organoborate intermediate for Suzuki coupling reactions, characterized in that, include: Compound A was dissolved in solvent 1 under inert atmosphere and stirred at -30 ~ -28 o C under low temperature environment, reacted with B(OR 3 )3 at room temperature under the action of strong base, and then acidified to generate intermediate compound B; Intermediate compound B is reacted with R 2 (OH) n at room temperature to form an organic boronic acid ester intermediate compound (II) as shown in the following chemical equation: The molar ratio of compound A to the base is 1:1.0 to 1:1.
5. The molar ratio of compounds A and B (OR 3 )3 is 1 : 1.5 to 1 : 3.0; Compound B and R 2 (OH) n at a molar ratio of 1 : 1.0 to 1 : 1.5; X 1 is a hydrogen atom or a nitro group, R 1 is any one of a hydrogen atom, a C1-C20 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted thienyl group, R 2 (OH) n (n = 1 or 2) is a mono- or dihydric alcohol; The desiccant is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate, silica gel, and anhydrous calcium chloride.
2. The production method according to claim 1, characterized by, When n is 1, R 2 The alkyl group remaining after removing two hydroxyl groups from a C1-C10 diol; when n is 2, R 2 It is any one of the alkyl, substituted or unsubstituted benzyl groups remaining after the removal of the hydroxyl group from a monohydric alcohol in C1-C10.
3. The preparation method according to claim 2, characterized in that, The alkyl groups remaining after removing two hydroxyl groups from C1-C10 diols are ethylenediyl, propylenediyl, butyldiyl, neopentyldiyl, or pinacol, while the alkyl groups remaining after removing hydroxyl groups from C1-C10 monools are methyl, ethyl, propyl, or isopropyl.
4. The preparation method according to claim 1, characterized in that, The strong base is n-butyllithium, diisopropylaminolithium, or sodium hydride, and the acid used for acidification is any one of acetic acid, oxalic acid, sulfuric acid, and hydrochloric acid.
5. The preparation method according to claim 1, characterized in that, Solvent 1 is n-hexane or tetrahydrofuran, and solvent 2 is n-hexane, tetrahydrofuran, petroleum ether, dichloromethane, or ethyl acetate.
6. The application of the organoboroate intermediate compound (II) obtained by the preparation method according to claims 1-5 in the preparation of DA'D units of Y-series receptors.
7. A method for preparing the DA'D unit of a Y-series receptor, using the organoboroate intermediate for the Suzuki coupling reaction as described in any one of claims 1-5 as a reactant, characterized in that, include: Under an inert atmosphere, compound (II), BT derivative C, and a base are coupled together in the presence of a catalyst to generate a compound with structure (I). Its chemical reaction formula is shown below: wherein X 2 is a hydrogen atom or a nitro group, and when X 1 is a hydrogen atom, X 2 is a nitro group, when X 1 is a nitro group, X 2 is a hydrogen atom; The molar ratio of BT derivative C to compound (II) is 1:2 to 1:2.4; The molar ratio of BT derivative C to catalyst is 1:0.01 to 1:0.05, and the catalyst is a palladium catalyst; The molar ratio of BT derivative C to base is 1:2.5 to 1:3.
0.
8. The method for preparing the DA'D unit of the Y-series receptor according to claim 7, characterized in that, The alkali is any one of NaHCO3, KHCO3, Na2CO3, K2CO3, Cs2CO3, CH3COONa, CH3COOK, NaOH, KOH, K3PO4, triethylamine, and diisopropylethylamine.
9. The method for preparing the DA'D unit of the Y-series receptor according to claim 7, characterized in that, The palladium catalyst is any one of bis(triphenylphosphine) palladium dichloride, tetra(triphenylphosphine) palladium, palladium acetate, DPPF palladium dichloride, and palladium chloride.
10. The method for preparing the DA'D unit of the Y-series receptor according to claim 7, characterized in that, Solvent 3 is any one of tetrahydrofuran, toluene, DMF or dioxane and water in a mixed system, wherein the volume ratio of tetrahydrofuran, toluene, DMF or dioxane and water in the mixed system is 10:1 to 1:1.