N-heterocyclic carbene compound and use thereof

Abstract

Disclosed in the present invention are an N-heterocyclic carbene compound and the use thereof. Provided in the present invention is a compound as represented by formula I. The N-heterocyclic carbene compound of the present invention has a novel structure, and has a good application prospect in monovalent copper-catalyzed silylallylation reactions.

Description

Nitrogen heterocyclic carbene compounds and their applications

[0001] This application claims priority to Chinese Patent Application No. 2024112025535, filed on August 29, 2024. The entire contents of the aforementioned Chinese patent application are incorporated herein by reference. Technical Field

[0002] This invention belongs to the field of organic synthesis, specifically relating to a class of nitrogen heterocyclic carbene compounds and their applications. Background Technology

[0003] Transition metal asymmetric catalysis is one of the most efficient and rapid methods for constructing chiral compounds, and chiral ligands play a crucial role in this process. Chiral nitrogen-heterocyclic carbene ligands have been extensively studied and developed due to their strong σ-electron-donating ability, structural stability, and ease of modular synthesis. (Dalton Trans., 2021, 50, 17467–17477.)

[0004] The synthesis of chiral nitrogen heterocyclic carbenes often requires the use of chiral amines as chiral precursors. Currently, the most extensive research focuses on nitrogen heterocyclic carbene ligands based on chiral 1,2-diphenylethylenediamine as the backbone. By changing the groups attached to the nitrogen atom, a series of five-membered ring nitrogen heterocyclic carbene ligands can be synthesized (J.Am.Chem.Soc.2017,139,9317–9324.). Professor Sawamura introduced phenolic hydroxyl groups as auxiliary coordinating groups to the substituents on the nitrogen atom (J.Am.Chem.Soc.2014,136,13932–13939.). In 2010, Professor McQuade also used chiral 1,2-diphenylethylenediamine as the chiral source to synthesize six-membered ring nitrogen heterocyclic carbene ligands. (Org. Lett., 2010, 12, 5008-5011.) Secondly, a series of nitrogen heterocyclic carbene ligands with chiral side chains can be synthesized by using α-chiral primary amines as chiral sources, which can be used in ruthenium-catalyzed asymmetric hydrogenation reactions of olefins. (J.Am.Chem.Soc.2020,142,7100–7107.) In 2011, Professor Gawley used C2-symmetric aniline with a bipolar center at the benzylic position as a chiral source to synthesize a C2-symmetric chiral nitrogen heterocyclic carbene ligand, which was then used in the copper-catalyzed hydrosilylation of alkyl ketones (J.Am.Chem.Soc.2011,133,49,19680–19683.). Professor Shih-Liang Shih further modified the skeleton by adding a rigid aromatic ring (Angew.Chem.,Int.Ed.,2018,57,1376–1380.). α-amino alcohols derived from α-amino acids can also be used as chiral sources for the synthesis of nitrogen heterocyclic carbenes, and have been successfully used in palladium-catalyzed asymmetric CH bond activation reactions (Angew. Chem. Int. Ed. 2021, 60, 7245–7250.).

[0005] However, most widely used nitrogen-containing heterocyclic carbenes currently suffer from difficulties in modifying their chiral source (e.g., 1,2-diphenylethylenediamine), hindering their serial synthesis and preventing precise control over steric hindrance and electronic properties. Therefore, designing chiral nitrogen-containing heterocyclic carbene ligands with easily modifiable chiral groups, convenient modular synthesis, and multiple control sites is of great significance.

[0006] The catalytic system of chiral nitrogen-heterocyclic carbenes and monovalent copper can realize the asymmetric allylation of silicon. In 2013, Professor Oestreich (Angew. Chem. Int. Ed. 2013, 52, 4650–4653.) and Professor Hayashi (J. Org. Chem. 2013, 78, 5007-5017.) reported monovalent copper-catalyzed asymmetric silylation reactions using different nitrogen-heterocyclic carbenes as ligands. However, both reactions use allyl phosphates as substrates, resulting in poor atom economy. When using more inexpensive and readily available allyl chloride as a substrate, the enantioselectivity control is poor. Therefore, developing a highly active nitrogen-heterocyclic carbene ligand to realize silylation reactions using allyl chloride as a substrate is of great significance. Summary of the Invention

[0007] The technical problem this invention aims to solve is to overcome the limitation of the limited types of ligands in copper-catalyzed silylation reactions in existing technologies. This invention provides a class of nitrogen-containing heterocyclic carbene compounds and their applications. The compounds of this invention show promising application prospects in monovalent copper-catalyzed silylation reactions.

[0008] This invention provides a compound as shown in Formula I.

[0009] in,

[0010] X is BF4 - or Cl - ;

[0011] R 1 It is a C1-C6 alkyl, C1-C6 alkoxy or C6-C 14 aryl;

[0012] R 2 For any one, two, or three Rs 2-1 Replacement C6-C 10 aryl or -CHR 2-2 R 2-3 ;

[0013] R 2-1 Independently, one, two, or three Rs can be selected. 2-1-1 Substituted C1-C6 alkyl groups, optionally with one, two, or three R... 2-1-2 Substituted C1-C6 alkoxy groups, C6-C 10 aryl or hydroxyl groups;

[0014] R 2-1-1 and R 2-1-2 Halogens are independent of each other;

[0015] R2-2 For C6-C 10 aryl;

[0016] R 2-3 For any one, two, or three Rs 2-3-1 Substituted C1-C6 alkyl groups;

[0017] R 2-3-1 Independently, it is a hydroxyl group;

[0018] R 3 For any one, two, or three Rs 3-1 Replacement C6-C 10 aryl;

[0019] R 3-1 It is a C1-C6 alkyl, C1-C6 alkoxy or C6-C 10 Aryl groups.

[0020] In one aspect of the present invention, the C1-C6 alkyl group and the C1-C6 alkyl group of each of the substituted C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; preferably methyl, ethyl, tert-butyl or isopropyl.

[0021] In one embodiment of the present invention, the C1-C6 alkoxy group and the substituted C1-C6 alkoxy group are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; preferably methoxy.

[0022] In one aspect of the present invention, R 1 In the context, the C6-C 14 The aryl group is independently phenyl or

[0023] In one embodiment of the present invention, each of the C6-C 10 aryl and each of the substituted C6-C 10 C6-C in aryl 10 The aryl group can be phenyl or naphthyl, for example, phenyl.

[0024] In one aspect of the invention, the halogen is independently fluorine, chlorine, bromine, or iodine; preferably fluorine.

[0025] In one embodiment of the present invention, X is BF4. - .

[0026] In one aspect of the present invention, R 1 It is a C1-C6 alkyl or C6-C 14 The aryl group; preferably a C1-C6 alkyl group.

[0027] In one aspect of the present invention, R 2 For 1, 2 or 3 R 2-1 Replacement C6-C 10 Aryl groups, for example

[0028] In one aspect of the present invention, R 2-1 Independently, one, two, or three Rs can be selected. 2-1-1 Substituted C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 The aryl or hydroxyl group; preferably a C1-C6 alkyl group.

[0029] In one aspect of the present invention, R 3-1 It is a C1-C6 alkyl or C1-C6 alkoxy group.

[0030] In one aspect of the present invention, R 1 Methyl, phenyl or

[0031] In one aspect of the present invention, R 2 for

[0032] In one aspect of the present invention, R 3 for

[0033] In one aspect of the present invention, the compound represented by Formula I is a compound represented by Formula I-1 or Formula I-2.

[0034] Among them, R 1 R 2-1 and R 3 The definition is as described in any embodiment of this invention;

[0035] In one aspect of the present invention, the compound represented by Formula I has any of the following structures:

[0036] The present invention also provides a compound as shown in Formula II.

[0037] Among them, R 1 R 2 and R 3 The definition is as described in any embodiment of this invention.

[0038] In one aspect of the present invention, the compound represented by Formula II has any of the following structures:

[0039] The present invention also provides the use of compounds as shown in Formula I and / or as shown in Formula II as catalysts in silylation reactions.

[0040] In one aspect of the present invention, the silylation reaction includes the following steps: in a solvent, in the presence of a catalyst and a base, compound A and compound B undergo a silylation reaction to prepare compound C;

[0041] The catalyst is “cuprous chloride and a compound as described above as shown in Formula I” and / or “a compound as described in any embodiment of the present invention as shown in Formula II”.

[0042] The solvent is a conventional solvent for this type of reaction in the art; preferably an ether solvent; more preferably tetrahydrofuran.

[0043] The base is a conventional base for this type of reaction in the art; preferably an alkali metal salt of an alcohol; more preferably sodium methoxide.

[0044] The molar ratio of compound B to compound A is a conventional molar ratio for this type of reaction in the art; preferably (1.2-1.8):1; more preferably 1.5:1.

[0045] The molar ratio of cuprous chloride to the compound shown in Formula I is a conventional molar ratio for this type of reaction in the art; preferably (0.8-1.2):1; more preferably 1:1.

[0046] The molar ratio of the catalyst to compound A is a conventional molar ratio for this type of reaction in the art; preferably (8-12):100; more preferably 10:100, wherein the amount of the catalyst is calculated as the sum of the compounds shown in Formula I and the compounds shown in Formula II.

[0047] The molar ratio of the base to the compound A is a conventional molar ratio for this type of reaction in the art; preferably (1.2-1.8):1; more preferably 1.5:1.

[0048] The mass-to-volume ratio of compound A to the solvent is a conventional mass-to-volume ratio for this type of reaction in the art; preferably (0.012-0.018) g / mL; more preferably 0.015 g / mL.

[0049] The reaction time for the silanization reaction is the conventional reaction time for this type of reaction in the art; preferably 8-16 hours; more preferably 12 hours.

[0050] The reaction temperature of the silylated reaction is the conventional reaction temperature for this type of reaction in the art; preferably -5 to 5°C; more preferably 0°C.

[0051] In one embodiment of the present invention, the silylation reaction further includes the following post-processing steps: quenching (e.g., acetic acid quenching) and rotary drying.

[0052] In one embodiment of the present invention, the reactants for the silylation reaction are the solvent, the cuprous chloride, the compound as shown in Formula I, the base, the compound A, and the compound B.

[0053] The present invention also provides a single crystal of the compound shown in Formula II-1.

[0054] The single crystal belongs to the orthorhombic crystal system, space group P212121, and its unit cell parameters are: α=γ=β=90°, unit cell volume The number of asymmetric units within the unit cell is Z = 8, and the crystal density is 1.152 g / cm³. 3 .

[0055] definition

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Furthermore, the following definitions are set forth to illustrate and define the meaning and scope of the various terms used to describe this invention.

[0057] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0058] The term "alkyl" refers to a straight-chain or branched alkyl group having a specified number of carbon atoms (e.g., C1-C6). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, etc.

[0059] The term "alkoxy" refers to the group R. Z -O-, where R Z It is an alkyl group as defined above.

[0060] The term "aryl" refers to an aryl group having a specified number of carbon atoms in its ring (e.g., C6-C). 10 Or C6-C 14 Aromatic rings, whose ring atoms consist solely of carbon atoms, can be fused or monocyclic. Examples include benzene rings, naphthalene rings, or...

[0061] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0062] The reagents and raw materials used in this invention are all commercially available.

[0063] The significant advantages of this invention are: it provides a class of nitrogen-containing heterocyclic carbene compounds and their applications. These nitrogen-containing heterocyclic carbene compounds exhibit novel structures and show promising application prospects in monovalent copper-catalyzed silylation reactions. Attached Figure Description

[0064] Figure 1 shows the single-crystal diffraction pattern of Cu-NHC. Detailed Implementation

[0065] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0066] Example 1: Synthesis of compounds YC-1 to YC-11, YC-13 to YC-17, and YC-19 to YC-21:

[0067] (1) Synthesis of intermediate 1 and similar intermediates

[0068] Experimental Procedure: A dry 100 mL double-necked flask equipped with a suitable magnetic magnet was used. 6-Methyl-2-chloroquinoline (10 mmol, 1.0 equiv), phenylboronic acid (12 mmol, 1.2 equiv), and sodium carbonate (50 mmol, 5.0 equiv) were added sequentially. The reaction flask was then transferred to a glove box, and tetrakis(triphenylphosphine)palladium (0.2 mmol, 0.02 equiv) was added. After the addition was complete, the flask was removed from the glove box, and ultra-dry 1,4-dioxane (40 mL, 0.2 M) and degassed water (10 mL, 0.2 M) were added. The mixture was heated to 105 °C and reacted for 8 h. After TLC confirmation of reaction completion, the mixture was allowed to cool naturally to room temperature. The mixture was filtered through diatomaceous earth, and the organic phase was collected. The organic phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was evaporated. The purified product was then purified by silica gel column chromatography to obtain 2.01 g of the target product 1, with a yield of 92%.

[0069] When synthesizing other similar structures in this invention, the intermediates in this step of YC-2, YC-3, YC-4, YC-20, and YC-21 are prepared using the same method as compound 1 above. For the synthesis of the intermediates in this step of compounds YC-5 to YC-19 (except YC-12 and YC-18), phenylboronic acid is replaced with other compounds, and the corresponding intermediates can be prepared using the same method as intermediate 1 above. See Table 1 below for details:

[0070] Table 1

[0071] (2) Synthesis of intermediate 2 and similar intermediates

[0072] Experimental Procedure: A dry 50 mL egg-shaped flask fitted with a suitable magnetic magnet was used. Compound 1 (3 mmol, 1.0 equiv), hesperidin (7.5 mmol, 2.5 equiv), and chiral phosphate CPA (0.06 mmol, 0.02 equiv) were added sequentially. The mixture was purged with nitrogen three times. Ultra-dry toluene (Tol, 8 mL, 0.38 M) was added, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, the mixture was filtered through diatomaceous earth, and the organic phase was collected. The solvent was evaporated, and the mixture was purified by silica gel column chromatography to obtain 650 mg of target product 2, with a yield of 97%. Compound 2 had an ee value >99% as determined by high-performance liquid chromatography. (Characteristic data are the same as in J. Org. Chem. 2023, 88, 3335–3339)

[0073] When synthesizing other similar structures in this invention, the intermediates in this step of YC-2, YC-3, YC-4, YC-20 and YC-21 are prepared using the same method as compound 1 above. For the synthesis of intermediates in this step of compounds YC-5 to YC-19 (except YC-12 and YC-18), compound 1 is replaced with the corresponding intermediate in Table 1 above, and the corresponding intermediate is prepared using the same method as intermediate 2, as shown in Table 2 below.

[0074] Table 2

[0075] (3) Synthesis of intermediate 3 and similar intermediates

[0076] Experimental procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 2 (3 mmol, 1.0 equiv), purge with nitrogen three times, add DCM (15 mL, 0.2 M), and after the addition is complete, lower the temperature to 0 °C and add NBS (N-bromosuccinimide, 3.15 mmol, 1.05 equiv) in three portions. React at this temperature overnight. After the reaction is complete, evaporate the solvent, and separate by column chromatography to obtain 524 mg of the target product 3, with a yield of 58%.

[0077] When synthesizing other similar structures in this invention, the intermediates in this step of YC-2, YC-3, YC-4, YC-20, and YC-21 are prepared using the same method as intermediate 3 described above. For the synthesis of intermediates in this step of compounds YC-5 to YC-19 (except for YC-12 and YC-18), intermediate 2 is replaced with the corresponding intermediate described above, and the corresponding intermediates are prepared using the same method as intermediate 3. See Table 3 below for details:

[0078] Table 3

[0079] (4) Synthesis of intermediate 4 and similar intermediates

[0080] Experimental Procedure: A dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet was used. Pd2(dba)3 (tris(dibenzylacetone)palladium, 0.05 mmol, 0.03 equiv), X-Phos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 0.10 mmol, 0.06 equiv), and sodium tert-butoxide (3.13 mmol, 1.8 equiv) were added sequentially. The flask was removed from the glove box, and ultra-dry toluene (8 mL, 0.22 M) was added. After complexation at room temperature for 5 min, trimethylaniline (2.1 mmol, 1.2 equiv) and compound 3 (1.75 mmol, 1.0 equiv) were added sequentially. The reaction was carried out at 90 °C for 3 h. After complete conversion of the starting material, the mixture was filtered through diatomaceous earth, the solvent was evaporated, and the product was purified by silica gel column chromatography to obtain 564 mg of the target product 4, with a yield of 91%.

[0081] When synthesizing other similar structures in this invention, for the synthesis of intermediates in this step of compounds YC-2 to YC-21 (except for YC-12 and YC-18), intermediate 3 or the corresponding intermediates mentioned above are used, either trimethylaniline or replaced with the corresponding structure, and the corresponding intermediates are prepared using the same method as intermediate 4. See Table 4 below for details:

[0082] Table 4:

[0083] (5) Synthesis of compounds YC-1 to YC-11, compounds YC-13 to YC-17 and compounds YC-19 to YC-21

[0084] Experimental Procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 1.58 mmol (1.0 equiv), 4 mL (0.4 M) of THF, and 2.0 mmol (1.3 equiv) of 1 M hydrochloric acid in methanol. After addition, stir at room temperature for 10 min, then evaporate the solvent. Add ammonium tetrafluoroborate (4.74 mmol, 3.0 equiv) and trimethyl orthoformate (5 mL, 0.3 M), and heat to 100 °C for 3 h. After the reaction is complete, evaporate the solvent, and purify by silica gel column chromatography to obtain 530 mg of the target product YC-1, with a yield of 74%.

[0085] When synthesizing other similar structures in this invention (excluding YC-2 to compounds YC-21, YC-12 and YC-18), intermediate 4 is replaced with the corresponding intermediate in Table 4 above, and the same preparation method as YC-1 is used to prepare the corresponding compounds YC-2 to YC-21 (excluding YC-12 and YC-18), as shown in Table 5 below.

[0086] Table 5

[0087] Example 2: Synthesis of compounds YC-12 and YC-18

[0088] (1) Synthesis of intermediate 5 and similar intermediates

[0089] Experimental Procedure: A dry 100 mL double-necked flask equipped with a suitable magnetic magnet was used. 6-Bromoquinoline (17.3 mmol, 1.0 equiv), phenylboronic acid (22.5 mmol, 1.3 equiv), and potassium carbonate (52 mmol, 3.0 equiv) were added sequentially. The reaction flask was then transferred to a glove box, and tetrakis(triphenylphosphine)palladium (0.87 mmol, 0.05 equiv) was added. After the addition was complete, the flask was removed from the glove box, and ultra-dry ethylene glycol dimethyl ether (20 mL, 0.58 M) and degassed water (10 mL, 0.58 M) were added. The mixture was heated to 105 °C and reacted for 8 h. After TLC confirmation of reaction completion, the mixture was allowed to cool naturally to room temperature. The mixture was filtered through diatomaceous earth, and the organic phase was collected. The phase was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was evaporated. The purified product was then purified by silica gel column chromatography to yield 3.52 g of the target product 5, with a yield of 100%.

[0090] For compound YC-18, the phenylboronic acid in the reaction needs to be replaced with 9-anthraylboronic acid, and the corresponding compound is prepared using the same method as compound 5.

[0091] (2) Synthesis of intermediate 6 and similar intermediates

[0092] Experimental Procedure: Take a dry 100 mL double-necked flask equipped with a suitable magnetic magnet, add 5 (17 mmol, 1.0 equiv), purge with nitrogen three times, and dissolve in toluene (17 mL, 0.58 M). Slowly add 3,5-xylmethylmagnesium bromide (2 M, 24 mmol, 1.4 equiv) dropwise at room temperature. After addition, raise the temperature to 125 °C and react for 12 h. After the reaction is complete, quench with saturated ammonium chloride, separate the phases, extract the aqueous phase with ethyl acetate, combine the organic phases, wash with saturated sodium chloride solution, dry to anhydrous sodium sulfate, evaporate to dryness, and purify by silica gel column chromatography to obtain 2.21 g of the target product 6, yield 42%.

[0093] When synthesizing other similar structures in this invention (compound YC-18), intermediate 5 is replaced with the corresponding structure described above. Using the same preparation method as intermediate 6, the corresponding intermediate was prepared.

[0094] (3) Synthesis of intermediate 7 and similar intermediates

[0095] Experimental Procedure: A dry 50 mL egg-shaped flask fitted with a suitable magnetic magnet was used. Compound 6 (4 mmol, 1.0 equiv), hesperidin (10.0 mmol, 2.5 equiv), and chiral phosphoric acid CPA (0.08 mmol, 0.02 equiv) were added sequentially. The mixture was purged with nitrogen three times, and ultra-dry toluene (8 mL, 0.5 M) was added. The reaction was allowed to proceed overnight at room temperature. After the reaction was complete, the mixture was filtered through diatomaceous earth, and the organic phase was collected. The solvent was evaporated, and the mixture was purified by silica gel column chromatography to obtain 1.35 g of the target product 7, with a yield >99%. The ee value of compound 7 was determined by high-performance liquid chromatography to be >99%.

[0096] When synthesizing other similar structures in this invention (compound YC-18), intermediate 6 is replaced with the corresponding structure described above. The corresponding compound was prepared using the same preparation method as intermediate 7.

[0097] (4) Synthesis of intermediate 8 and similar intermediates

[0098] Experimental procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 7 (4 mmol, 1.0 equiv), purge with nitrogen three times, add DCM (10 mL, 0.25 M), and after the addition is complete, lower the temperature to 0 °C and add NBS (4.2 mmol, 1.05 equiv) in three portions. React at this temperature overnight. After the reaction is complete, evaporate the solvent, and separate by column chromatography to obtain 1.16 g of the target product 8, with a yield of 74%.

[0099] When synthesizing other similar structures in this invention (compound YC-18), intermediate 7 is replaced with the corresponding structure described above. Using the same preparation method as intermediate 8, the corresponding intermediate was prepared.

[0100] (5) Synthesis of intermediate 9 and similar intermediates

[0101] Experimental Procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, and add Pd2(dba)3 (0.15 mmol, 0.05 equiv), X-Phos (0.30 mmol, 0.10 equiv), and sodium tert-butoxide (5.40 mmol, 1.80 equiv) sequentially. Remove from the glove box, add ultra-dry toluene (10 mL, 0.33 M), and complex at room temperature for 5 min. Then add mesitylene (3.3 mmol, 1.1 equiv) and compound 8 (3.0 mmol, 1.0 equiv) sequentially. After the addition is complete, react at 90 °C for 3 h. After the starting material is completely converted, filter with diatomaceous earth, evaporate the solvent, and purify by silica gel column chromatography to obtain 1.21 g of target product 9, with a yield of 91%.

[0102] When synthesizing other similar structures in this invention (compound YC-18), intermediate 8 is replaced with the corresponding structure described above. Replace with The corresponding intermediate was prepared using the same preparation method as compound 9.

[0103] (6) Synthesis of compounds YC-12 and YC-18

[0104] Experimental Procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 2.7 mmol (1.0 equiv), THF (4 mL, 0.68 M), and 1 M hydrochloric acid-methanol solution (3.5 mmol, 1.3 equiv). After addition, stir at room temperature for 10 min, then evaporate the solvent. Add ammonium tetrafluoroborate (8.1 mmol, 3.0 equiv) and trimethyl orthoformate (8 mL, 0.34 M), and heat to 100 °C for 3 h. After the reaction is complete, evaporate the solvent, and purify by silica gel column chromatography to obtain 716 mg of the target product YC-12, with a yield of 49%.

[0105] When synthesizing other similar structures in this invention (compound YC-18), compound 9 is replaced with the corresponding structure described above. Compound YC-18 was prepared using the same preparation method as compound YC-18.

[0106] Example 3 Synthesis of YC-22-25

[0107] (1) Synthesis of intermediate 10 and similar intermediates

[0108] Experimental Procedure: Take a dry 50 mL egg-shaped flask fitted with a suitable magnetic magnet, and add 2-aminophenol (10 mmol, 1.0 equiv), imidazole (15 mmol, 1.5 equiv), and DMF (15 mL, 0.67 M) sequentially. Lower the temperature to 0 °C, add TBSCl (tert-butyldimethylchlorosilane, 12 mmol, 1.2 equiv), and allow the mixture to react at room temperature overnight. After the reaction is complete, extract with diethyl ether, wash with saturated NaCl, dry under anhydrous sodium sulfate, evaporate the solvent, and purify by silica gel column chromatography to obtain 2.03 g of the target product 10, with a yield of 91%.

[0109] In other synthetic examples of this invention, 2-aminophenol in this step needs to be replaced with 6-amino-2-methylphenol, 2-amino-5-methylphenol, or o-amino-p-cresol; the corresponding intermediates are prepared using the same preparation method as intermediate 10.

[0110] (2) Synthesis of intermediate 11 and similar intermediates

[0111] Experimental Procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, and add Pd₂(dba)₃ (0.06 mmol, 0.03 equiv), X-Phos (0.12 mmol, 0.06 equiv), and sodium tert-butoxide (3.6 mmol, 1.8 equiv) sequentially. Remove from the glove box, add ultra-dry toluene (6 mL, 0.33 M), and complex at room temperature for 5 min. Then add compound 10 (2.2 mmol, 1.1 equiv) and compound 3 (2.0 mmol, 1.0 equiv) sequentially. After the addition is complete, react at 90 °C for 3 h. After complete conversion of the starting material, filter with diatomaceous earth, evaporate the solvent, and purify by silica gel column chromatography to obtain 820 mg of the target product 11, with a yield of 92%.

[0112] When synthesizing other similar structures in this invention, intermediate 10 is replaced with Intermediate 11 was prepared using the same preparation method.

[0113] (3) Synthesis of compounds YC-22 to YC-25

[0114] Experimental Procedure: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 11 (1.9 mmol, 1.0 equiv), THF (4 mL, 0.48 M), and 1 M hydrochloric acid-methanol solution (7.6 mmol, 4.0 equiv). After addition, react overnight at room temperature. After the reaction is complete, evaporate the solvent by rotary evaporation, heat to dryness under oil pump, add ammonium tetrafluoroborate (5.7 mmol, 3.0 equiv) and trimethyl orthoformate (5 mL, 0.38 M), and heat to 100 °C for 3 h. After the reaction is complete, evaporate the solvent by rotary evaporation, and purify by silica gel column chromatography to obtain 463 mg of the target product YC-22, with a yield of 57%.

[0115] When synthesizing other similar structures in this invention, compound 11 is replaced with Using the same preparation method as YC-22, the corresponding [product / process] was prepared.

[0116] Example 4: Synthesis of compound YC-26

[0117] (1) Synthesis of intermediate 12

[0118] Experimental Procedure: Take a dry 100 mL egg-shaped flask fitted with a suitable magnetic magnet, and add D-phenylglycine (10 mmol, 1.0 equiv), DMAP (dimethylaminopyridine, 1 mmol, 0.1 equiv), triethylamine (20 mmol, 2.0 equiv), and DCM (15 mL, 0.67 M) sequentially. Then add TBSCl (10 mmol, 1.0 equiv) all at once. After the addition is complete, react at room temperature overnight. After the reaction is complete, evaporate the solvent, and purify by silica gel column chromatography to obtain 1.86 g of the target product 12, with a yield of 74%.

[0119] (2) Synthesis of intermediate 14

[0120] Note: The synthesis steps of intermediate 13 are the same as those of intermediate 3, and its ee value is >99%.

[0121] Experimental Procedure: Take a dry 50 mL double-necked flask equipped with a suitable magnetic magnet, and add Pd2(dba)3 (0.06 mmol, 0.06 equiv), rac-BINAP (2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, 0.12 mmol, 0.12 equiv), and sodium tert-butoxide (2.0 mmol, 2.0 equiv) sequentially. Remove from the glove box, add ultra-dry toluene (5 mL, 0.2 M), and complex at room temperature for 5 min. Then add compound 12 (1.2 mmol, 1.2 equiv) and compound 13 (1.0 mmol, 1.0 equiv) sequentially. After the addition is complete, react at 125 °C for 3 h. After the starting material is completely converted, filter with diatomaceous earth, evaporate the solvent by rotary evaporation, and purify the target product 14 by silica gel column chromatography.

[0122] (3) Synthesis of compound YC-26

[0123] Experimental Procedure K: Take a dry 50 mL egg-shaped flask equipped with a suitable magnetic magnet, add 14 (1.0 mmol, 1.0 equivalent), THF (2 mL, 0.5 M), and 1 M hydrochloric acid methanol solution (3 mmol, 3.0 equivalent). After addition, react at room temperature for 2 h. After the reaction is complete, evaporate the solvent by rotary evaporation, heat to dryness under oil pump, add ammonium tetrafluoroborate (5.7 mmol, 3.0 equivalent) and trimethyl orthoformate (5 mL, 0.2 M), and heat to 100 °C for 3 h. After the reaction is complete, evaporate the solvent by rotary evaporation, and purify by silica gel column chromatography to obtain 325 mg of the target product YC-26, with a yield of 67%.

[0124] Example 5. Monovalent copper-catalyzed silylation reaction

[0125] Experimental Procedure: Take a dry 25 mL Schenk tube fitted with a suitable magnetic magnet, and add cuprous chloride (0.01 mmol, 0.1 equiv), ligand (0.01 mmol, 0.1 equiv), and sodium methoxide (0.15 mmol, 1.5 equiv) sequentially. Remove from the glove box, add THF (1 mL, 0.1 M), and complex at room temperature for 20 min. Then lower the temperature to 0 °C, and add borosilicate reagent (0.15 mmol, 1.5 equiv) and cinnamyl chloride (0.1 mmol, 1.0 equiv) sequentially. After the addition is complete, react at this temperature for 12 h. After the reaction is complete, add 20 μL of acetic acid to quench the reaction, evaporate the solvent to dryness, add nitromethane as an internal standard, determine the reaction yield using NMR, and determine the enantioselectivity of the reaction using HPLC. Product Data: 1 H NMR(500MHz, CDCl3)δ7.40–7.26(m,5H),7.21–7.13(m,2H),7.11–7.04(m,1H),6.98–6.84(m,2H), 6.10(dt,J=18.7,10.0Hz,1H),5.01–4.81(m,2H),3.14(d,J=9.6Hz,1H),0.26(s,3H),0.24(s,3H). 13 C NMR (126MHz, CDCl3) δ141.62,137.74,136.70,134.32,129.11,128.13,127.45,124.71,113.03,44.27,-4.31,-4.89.

[0126] Optical rotation:[α] D 25 = -8.68 (c = 1.080, CHCl3).

[0127] The yields and ee values ​​for different ligands are as follows:

[0128] Example 6. Synthesis of copper-carbene complex

[0129] Take a dry 50 mL Schenk flask fitted with a suitable magnetic magnet and add YC-1 (1.0 mmol, 1.0 equiv) and cuprous chloride (1.1 mmol, 1.1 equiv). Separately, take a 25 mL egg-shaped flask and add potassium tert-butoxide (1.1 mmol, 1.1 equiv). After the additions are complete, remove the flask from the glove box. Add THF as a solvent to both the Schenk flask (3 mL, 0.33 M) and the egg-shaped flask (1.1 mL, 1.0 M), respectively. Cool to 0 °C, and add sodium tert-butoxide solution dropwise to the Schenk flask. After the addition is complete, raise the temperature to room temperature and react for 10 min. After the reaction is complete, remove the solvent from the system using an oil pump, add DCM (4 mL, 0.25 M) as a solvent, and react at room temperature for 16 h. After the reaction is complete, filter with diatomaceous earth under nitrogen protection, wash with a small amount of DCM, and remove the solvent using an oil pump to obtain 399 mg of the target product Cu-NHC, with a yield of 86%. The single-crystal testing conditions for Cu-NHC are shown in Table 6 below, the single-crystal data are shown in Table 7 below, and the single-crystal diffraction pattern is shown in Figure 1.

[0130] Table 6

[0131] Table 7

[0132] Example 7. Silicylation of copper-carbene complexes

[0133] The cuprous chloride and ligand in Example 5 were replaced with Cu-NHC, and the remaining reaction conditions were the same as in Example 5.

[0134] Ligand data

[0135] 1 H NMR(400MHz, CDCl3)δ8.68(s,1H),7.40–7.30(m,4H),7.17–7.11(m,2H),7 .05(s,1H),7.02(s,1H),6.90(s,1H),6.36–6.26(dd,1H),3.17(ddd,J=17 .2,6.5,4.5Hz,1H),3.00(ddd,J=16.9,8.6,4.4Hz,1H),2.70(m,J=13.3,8 .8,4.5Hz,1H),2.55–2.47(m,4H),2.35(s,3H),2.07(s,3H),1.88(s,3H).

[0136] 1313C NMR (101 MHz, CDCl3) δ 141.47, 139.67, 139.65, 139.21, 137.70, 136.21, 134.48, 134.46, 130.34, 130.21, 129.58, 129.37, 129.08, 128.32, 127.78, 126.67, 126.19, 125.78, 109.76, 59.07, 30.31, 22.11, 21.04, 21.00, 17.23, 17.14.

[0137] HRMS (ESI) m / z + [M - BF4]: calcd. 367.2169, found 367.2165.

[0138] IR (film): ν max (cm -1 ) 3128, 3034, 2925, 1609, 1537, 1503, 1455, 1300, 1276, 1204, 1058, 915, 841, 748, 703.

[0139] Optical rotation: [α] D 25 = 39.15 (c = 1.655, CHCl3).

[0140] 1 1H NMR (400 MHz, CDCl3) δ 8.69 (s, 1H), 7.59 (t, J = 7.8 Hz, 1H), 7.42–7.32 (m, 6H), 7.21–7.15 (m, 2H), 6.91 (s, 1H), 6.39 (dd, J = 6.6, 4.4 Hz, 1H), 3.24 (ddd, J = 17.0, 7.1, 4.5 Hz, 1H), 3.04 (ddd, J = 16.9, 8.2, 4.4 Hz, 1H), 2.76 (ddt, J = 13.0, 8.6, 4.3 Hz, 1H), 2.59–2.47 (m, 5H), 2.00 (p, J = 6.8 Hz, 1H), 1.22 (d, J = 6.7 Hz, 3H), 1.11 (d, J = 6.9 Hz, 3H), 1.08 (d, J = 6.8 Hz, 3H), 1.00 (d, J = 6.9 Hz, 3H).

[0141] 13 ​​​​C NMR(101MHz,CDCl3)δ147.37,145.68,139.81,139.53,137.77,132.07,131.86,129.35,129.16,127.78,127.62,126.86,126.28,125.99,125.31,124.45,109.65,59.21,30.41,28.86,28.51,24.48,24.43,23.96,23.54,22.20,21.24.

[0142] HRMS(ESI)m / z[M-BF4] + :calcd.409.2638,found 409.2634.

[0143] IR(film):ν max (cm -1 )3113,2966,2930,2871,1537,1458,1275,1204,1059,915,808,750,701.

[0144] Optical rotation:[α] D 25 =47.10(c=1.800,CHCl3).

[0145] 1 H NMR(400 MHz,CDCl3)δ8.91(s,1H),7.62(t,J=1.7 Hz,1H),7.52(d,J=1.7 Hz,2H),7.41–7.36(m,3H),7.32(s,1H),7.28–7.25(m,3H),6.25(dd,J=6.2,4.2 Hz,1H),3.16(dt,J=17.1,5.6 Hz,1H),3.10–2.99(m,1H),2.65(ddt,J=13.1,8.7,4.6 Hz,1H),2.57–2.48(m,4H),1.38(s,18H).

[0146] 13C NMR(101 MHz,CDCl3)δ154.03,139.18,138.16,137.25,133.01,130.34,129.35,129.16,128.07,126.73,126.52,125.62,124.55,118.96,110.43,59.18,35.26,31.18,30.14,22.30,21.33.

[0147] HRMS(ESI)m / z[M-BF4] + :calcd.437.2951,found 437.2948.

[0148] IR(film):ν max (cm -1 )3142,2963,2869,1594,1543,1478,1207,1059,914,837,764,750,709.

[0149] Optical rotation:[α] D 25 =106.15(c=1.825,CHCl3).

[0150] 1 H NMR(400 MHz,CDCl3)δ8.70(s,1H),7.53(t,J=7.7 Hz,1H),7.36(m,5H),7.28(d,J=7.5 Hz,1H),7.21–7.14(m,2H),6.91(s,1H),6.36(dd,J=6.3,4.4 Hz,1H),3.22(ddd,J=17.2,6.7,4.5 Hz,1H),3.03(ddd,J=16.9,8.3,4.4 Hz,1H),2.74(ddt,J=13.1,8.6,4.1 Hz,1H),2.59–2.41(m,5H),2.32(dt,J=15.5,7.6 Hz,1H),2.20(dt,J=15.1,7.5 Hz,1H),2.08(dq,J=14.9,7.5 Hz,1H),1.11(t,J=7.5 Hz,3H),0.99(t,J=7.6 Hz,3H).

[0151] 13C NMR(101 MHz,CDCl3)δ142.29,140.82,139.79,139.26,137.64,131.68,131.11,129.59,129.35,129.14,127.63,127.49,127.20,126.81,126.22,125.86,109.77,59.16,30.29,24.13,23.51,22.14,21.07,14.92,14.31.

[0152] HRMS(ESI)m / z[M-BF4] + :calcd.381.2325,found 381.2323.

[0153] IR(film):ν max (cm -1 )3126,2970,2936,2878,1537,1504,1456,1300,1058,915,730,702.

[0154] Optical rotation:[α] D 25 =39.85(c=2.025,CHCl3).

[0155] 1 H NMR(400 MHz,CDCl3)δ8.64(s,1H),7.32(s,1H),7.18(d,J=7.9 Hz,2H),7.08–7.03(m,3H),7.03(s,1H),6.90(s,1H),6.28(dd,J=6.4,4.4 Hz,1H),3.19(ddd,J=17.1,7.0,4.6 Hz,1H),3.03(ddd,J=17.1,8.3,4.5 Hz,1H),2.69(ddt,J=12.9,8.6,4.3 Hz,1H),2.54–2.46(m,4H),2.37(s,3H),2.33(s,3H),2.09(s,3H),1.89(s,3H).

[0156] 13C NMR(101 MHz,CDCl3)δ141.43,139.58,139.09,136.23,134.61,134.47,130.34,130.19,130.01,129.56,128.34,127.80,126.60,126.22,125.83,109.71,59.01,30.36,22.10,21.22,21.04,20.99,17.23,17.14.

[0157] HRMS(ESI)m / z[M-BF4] + :calcd.381.2325,found 381.2322.

[0158] IR(film):ν max (cm -1 )3127,2926,2862,1538,1504,1449,1300,1203,1192,1061,915,730.

[0159] Optical rotation:[α] D 25 =32.86(c=1.810,CHCl3).

[0160] 1 H NMR(400 MHz,CDCl3)δ8.67(s,1H),7.31(s,1H),7.08(s,1H),7.03(s,1H),6.98(s,1H),6.91(s,1H),6.72(s,2H),6.26(dd,J=6.2,4.4 Hz,1H),3.18(dt,J=17.0,5.6 Hz,1H),2.99(ddd,J=17.0,8.7,4.4 Hz,1H),2.70(ddt,J=13.2,8.7,4.5 Hz,1H),2.56–2.48(m,4H),2.37(s,3H),2.26(s,6H),2.11(s,3H),1.90(s,3H).

[0161] 13C NMR(101 MHz,CDCl3)δ141.45,139.57,139.23,139.08,137.59,136.31,134.37,130.67,130.31,130.24,129.57,128.38,127.82,126.59,125.89,123.90,109.69,59.09,30.29,22.12,21.21,21.15,21.04,17.23,17.00.

[0162] HRMS(ESI)m / z[M-BF4] + :calcd.395.2482,found 395.2478.

[0163] IR(film):ν max (cm -1 )3124,2923,1608,1538,1454,1198,1059,914,842,730.

[0164] Optical rotation:[α] D 25 =53.76(c=2.090,CHCl3).

[0165] 1 H NMR(400 MHz,CDCl3)δ8.69(s,1H),7.59(d,J=8.0 Hz,2H),7.54(d,J=7.2 Hz,2H),7.42(t,J=7.5Hz,2H),7.36–7.32(m,2H),7.25(d,J=7.9 Hz,2H),7.05(d,J=12.8 Hz,2H),6.92(s,1H),6.37(dd,J=6.3,4.4 Hz,1H),3.21(dt,J=17.2,5.4 Hz,1H),3.06(ddd,J=16.9,8.4,4.4 Hz,1H),2.73(ddt,J=13.2,8.8,4.4 Hz,1H),2.52(s,4H),2.36(s,3H),2.09(s,3H),1.91(s,3H).

[0166] 13C NMR(101 MHz,CDCl3)δ142.04,141.47,139.88,139.68,139.18,136.55,136.21,134.47,130.37,130.21,129.58,128.79,128.32,128.01,127.78,127.66,126.98,126.76,126.69,125.78,109.77,58.89,30.32,22.11,21.14,21.03,17.23,17.17.

[0167] HRMS(ESI)m / z[M-BF4] + :calcd.443.2482,found 443.2480.

[0168] IR(film):ν max (cm -1 )3123,3031,2924,1537,1487,1449,1300,1059,914,841,769,731,699.

[0169] Optical rotation:[α] D 25 =47.03(c=2.080,CHCl3).

[0170] 1 H NMR(400 MHz,CDCl3)δ8.66(s,1H),7.31(s,1H),7.09(s,1H),7.02(s,2H),6.91(s,1H),6.79(s,2H),6.28(dd,J=6.4,4.4 Hz,1H),3.19(ddd,J=17.1,7.0,4.6 Hz,1H),3.01(ddd,J=16.8,8.4,4.4 Hz,1H),2.72(ddt,J=13.2,8.7,4.5 Hz,1H),2.62–2.48(m,8H),2.37(s,3H),2.12(s,3H),1.89(s,3H),1.16(t,J=7.6Hz,6H).

[0171] 13C NMR(101 MHz,CDCl3)δ145.53,141.44,139.53,139.22,137.74,136.40,134.31,130.29,130.26,129.51,128.38,128.32,127.86,126.55,125.90,123.06,109.68,59.27,30.43,28.64,22.13,21.28,21.05,17.25,17.02,15.35.

[0172] HRMS(ESI)m / z[M-BF4] + :calcd.423.2795,found 423.2790.

[0173] IR(film):ν max (cm -1 )3124,2965,2931,2873,1604,1538,1461,1198,1059,914,853,730.

[0174] Optical rotation:[α] D 25 =47.29(c=1.835,CHCl3).

[0175] 1 H NMR(400 MHz,CDCl3)δ8.69(s,1H),7.87(d,J=8.5 Hz,1H),7.85–7.79(m,1H),7.78–7.71(m,1H),7.62(s,1H),7.53–7.47(m,2H),7.33(s,1H),7.26(s,1H),7.07(s,1H),7.01(s,1H),6.94(s,1H),6.54(t,J=5.4 Hz,1H),3.27–3.17(m,1H),3.03(ddt,J=15.9,8.0,4.7 Hz,1H),2.79(tt,J=8.6,4.2 Hz,1H),2.69–2.60(m,1H),2.54(s,3H),2.36(s,3H),2.11(s,3H),1.92(s,3H).

[0176] 13C NMR(101 MHz,CDCl3)δ141.54,139.73,139.34,136.37,134.83,134.45,133.32,133.20,130.47,130.32,129.61,128.39,128.15,127.91,127.70,126.98,126.95,126.75,126.41,125.89,122.98,109.86,59.32,30.24,22.21,21.31,21.11,17.31,17.20.

[0177] HRMS(ESI)m / z[M-BF4] + :calcd.417.2325,found 417.2324.

[0178] IR(film):ν max (cm -1 )3126,2925,1607,1538,1505,1444,1196,1060,914,854,730.

[0179] Optical rotation:[α] D 25 =42.60(c=1.972,CHCl3).

[0180] 1 H NMR(400 MHz,CDCl3)δ8.63(s,1H),7.31(s,1H),7.08(s,1H),7.04(s,1H),6.90(s,1H),6.81(s,2H),6.17(dd,J=6.9,4.2 Hz,1H),3.71(s,3H),3.20(ddd,J=17.4,7.3,4.6 Hz,1H),3.03(dq,J=17.0,4.5 Hz,1H),2.68(ddd,J=13.6,7.9,3.8 Hz,1H),2.55–2.47(s,4H),2.37(s,3H),2.22(s,6H),2.10(s,3H),1.90(s,3H).

[0181] 13C NMR(101 MHz,CDCl3)δ157.48,141.45,139.53,139.23,136.37,134.37,132.67,132.07,130.36,130.26,129.56,128.40,127.82,126.76,126.55,125.89,109.70,59.59,58.89,30.41,22.13,21.46,21.06,17.26,17.05,16.08.

[0182] HRMS(ESI)m / z[M-BF4] + :calcd.425.2587,found 425.2584.

[0183] IR(film):ν max (cm -1 )3122,2926,1538,1486,1300,1197,1147,1059,915,855,731.

[0184] Optical rotation:[α] D 25 =47.11(c=2.280,CHCl3).

[0185] 1 H NMR(400 MHz,CDCl3)δ8.61(s,1H),7.31(s,1H),7.07(s,1H),7.03(s,1H),6.90(s,1H),6.78(s,2H),6.18(dd,J=6.6,4.3 Hz,1H),3.19(ddd,J=16.9,7.3,4.6 Hz,1H),3.02(ddd,J=16.9,7.7,4.2 Hz,1H),2.68(ddt,J=12.9,8.5,4.5 Hz,1H),2.56–2.48(m,4H),2.37(s,3H),2.22(s,6H),2.14(s,3H),2.10(s,3H),1.90(s,3H).

[0186] 13C NMR(101 MHz,CDCl3)δ141.44,139.47,139.28,137.61,136.45,136.22,134.39,134.30,130.37,130.28,129.54,128.44,127.90,126.50,125.98,125.33,109.68,59.04,30.36,22.15,21.43,21.08,20.53,17.29,17.05,15.15.

[0187] HRMS(ESI)m / z[M-BF4] + :calcd.409.2638,found 409.2635.

[0188] IR(film):ν max (cm -1 )3126,2926,1537,1486,1444,1300,1195,1059,914,853,730.

[0189] Optical rotation:[α] D 25 =47.70(c=2.140,CHCl3).

[0190] 1 H NMR(400 MHz,CDCl3)δ8.72(s,1H),7.58–7.52(m,2H),7.48–7.43(m,2H),7.42–7.37(m,1H),7.24(s,1H),7.09(s,1H),7.05(s,1H),7.01(s,1H),6.79(s,2H),6.29(dd,J=6.6,4.3 Hz,1H),3.30(ddd,J=17.0,6.9,4.3 Hz,1H),3.12(ddd,J=17.0,8.1,4.3 Hz,1H),2.76(ddd,J=17.0,8.4,4.2 Hz,1H),2.59(ddt,J=13.8,6.7,3.3 Hz,1H),2.38(s,3H),2.28(s,6H),2.15(s,3H),1.95(s,3H).

[0191] 13C NMR(101 MHz,CDCl3)δ142.97,141.62,140.26,139.73,139.19,137.48,136.47,134.31,130.80,130.63,130.41,129.65,129.04,128.96,128.34,128.30,127.71,126.66,124.92,124.03,108.46,59.31,30.38,21.60,21.20,21.08,17.36,17.12.

[0192] HRMS(ESI)m / z[M-BF4] + :calcd.457.2638,found 457.2635.

[0193] IR(film):ν max (cm -1 )3123,3034,2923,1643,1537,1486,1214,1179,1059,913,855,766,731,700.

[0194] Optical rotation:[α] D 25 =28.28(c=2.085,CHCl3).

[0195] 1 H NMR(400 MHz,CDCl3)δ8.64(s,1H),7.31(s,1H),6.98(s,1H),6.92(s,1H),6.77(d,J=2.8 Hz,1H),6.75–6.70(m,3H),6.23(dd,J=6.3,4.3 Hz,1H),3.84(s,3H),3.18(ddd,J=17.0,7.0,4.7 Hz,1H),3.00(ddd,J=16.9,8.3,4.4 Hz,1H),2.70(ddt,J=13.1,8.7,4.3 Hz,1H),2.56–2.48(m,4H),2.26(s,6H),2.12(s,3H),1.91(s,3H).

[0196] 13C NMR(101 MHz,CDCl3)δ161.01,139.64,139.52,139.11,138.34,137.65,136.17,130.69,130.58,127.84,126.55,125.91,123.93,123.60,114.37,114.33,109.72,59.07,55.54,30.31,22.17,21.23,21.19,17.72,17.40.

[0197] HRMS(ESI)m / z[M-BF4] + :calcd.411.2431,found 411.2428.

[0198] IR(film):ν max (cm -1 )3123,2923,1600,1538,1327,1198,1160,1060,914,842,730.

[0199] Optical rotation:[α] D 25 =54.51(c=1.890,CHCl3).

[0200] 1 H NMR(400 MHz,CDCl3)δ8.67(s,1H),7.41(t,J=7.7 Hz,1H),7.33(s,1H),7.28(d,J=7.2 Hz,1H),7.24(d,J=7.6 Hz,1H),6.99(s,1H),6.91(s,1H),6.74(s,2H),6.24(dd,J=6.4,4.4 Hz,1H),3.19(ddd,J=17.0,6.1,3.6 Hz,1H),3.01(ddd,J=16.9,8.2,4.5 Hz,1H),2.71(dq,J=13.6,4.3 Hz,1H),2.57–2.50(m,4H),2.26(s,6H),2.15(s,3H),1.95(s,3H).

[0201] 13C NMR(101 MHz,CDCl3)δ139.65,139.21,139.13,137.58,136.88,134.77,131.21,130.99,130.72,130.17,129.69,128.92,127.87,126.65,125.99,123.96,109.68,59.17,30.32,22.16,21.28,21.19,17.38,17.12.

[0202] HRMS(ESI)m / z[M-BF4] + :calcd.381.2325,found 381.2322.

[0203] IR(film):ν max (cm -1 )3127,2924,1606,1537,1504,1475,1300,1198,1061,914,844,730.

[0204] Optical rotation:[α] D 25 =53.00(c=1.775,CHCl3).

[0205] 1 H NMR(400 MHz,CDCl3)δ8.57(s,1H),7.35–7.29(d,J=3.4 Hz,4H),7.01(s,1H),6.97(s,1H),6.86(s,2H),6.10(dd,J=7.4,4.2 Hz,1H),3.20(ddd,J=17.0,7.8,4.7 Hz,1H),3.06(ddd,J=17.0,7.3,4.6 Hz,1H),2.69–2.61(m,1H),2.58–2.49(s,4H),2.38(s,3H),2.29(s,6H),2.09(s,3H).

[0206] 13 C NMR(101 MHz,CDCl3)δ139.26,139.19,138.55,138.22,136.96,132.09,131.65,131.55,130.93,130.90,127.97,127.70,126.39,125.73,124.43,110.19,59.43,30.20,22.15,21.78,21.21,20.61,16.81.

[0207] HRMS(ESI)m / z[M-BF4] + :calcd.381.2325,found 381.2322.

[0208] IR(film):ν max (cm -1 )3140,2924,1609,1541,1505,1462,1301,1058,914,841,729.

[0209] Optical rotation:[α] D 25 =57.97(c=1.905,CHCl3).

[0210] 1 H NMR(400 MHz,CDCl3)δ8.72(s,1H),7.32(s,3H),7.30(s,1H),7.19(s,1H),7.01(s,1H),6.88(s,2H),6.05(dd,J=7.3,4.3 Hz,1H),3.16(ddd,J=17.1,7.7,4.8 Hz,1H),3.07(ddd,J=17.1,7.1,4.7 Hz,1H),2.64–2.48(m,5H),2.42(s,6H),2.29(s,6H).

[0211] 13 C NMR(101 MHz,CDCl3)δ140.77,139.17,139.12,137.85,136.77,133.26,132.14,130.99,130.20,128.07,126.46,125.61,124.60,122.12,110.44,59.44,30.14,22.22,21.81,21.22,21.14.

[0212] HRMS(ESI)m / z[M-BF4] + :calcd.381.2325,found 381.2324.

[0213] IR(film):ν max (cm -1 )2923,1610,1543,1505,1470,1215,1058,913,843,730.

[0214] Optical rotation:[α] D 25 =87.88(c=1.880,CHCl3).

[0215] 1 H NMR(400 MHz,CDCl3)δ8.63(s,1H),7.31(s,1H),7.26(d,J=2.1 Hz,1H),7.21(d,J=2.2 Hz,1H),6.98(s,1H),6.95(s,1H),6.75(s,2H),6.24(dd,J=6.5,4.3 Hz,1H),3.19(ddd,J=17.1,7.2,5.0 Hz,1H),3.01(ddd,J=16.9,8.4,4.4 Hz,1H),2.70(ddt,J=12.8,8.5,4.2 Hz,1H),2.59–2.48(m,4H),2.26(s,6H),2.15(s,3H),1.94(s,3H),1.35(s,9H).

[0216] 13 C NMR(101 MHz,CDCl3)δ154.46,139.47,139.33,139.10,137.63,136.12,134.02,130.68,130.34,128.40,127.87,126.76,126.54,125.98,125.92,123.99,109.81,59.11,34.73,31.09,30.34,22.16,21.33,21.19,17.66,17.41.

[0217] HRMS(ESI)m / z[M-BF4] + :calcd.437.2951,found 437.2949.

[0218] IR(film):ν max (cm -1 )3124,2964,2868,1604,1538,1461,1197,1060,914,842,730.

[0219] Optical rotation:[α] D 25 =49.80(c=1.725,CHCl3).

[0220] 1H NMR(400 MHz,CDCl3)δ8.70(s,1H),8.54(s,1H),8.06(dd,J=8.3,3.6 Hz,2H),7.57–7.36(m,7H),7.22(s,1H),7.17(d,J=2.1 Hz,1H),7.13(d,J=2.2 Hz,1H),7.07(s,1H),7.03(s,2H),6.33(dd,J=8.2,4.2Hz,1H),3.41(ddd,J=17.5,8.8,4.7 Hz,1H),3.27–3.18(m,1H),2.89–2.80(m,1H),2.76–2.64(m,1H),2.35(s,6H),2.25(s,3H),2.05(s,3H),1.24(s,9H).

[0221] 13 C NMR(101 MHz,CDCl3)δ154.53,140.43,139.95,139.37,137.18,136.18,134.32,133.77,131.23,131.08,130.46,130.40,130.02,129.28,128.72,128.43,128.29,128.05,127.68,126.91,126.57,126.44,126.01,125.97,125.64,125.43,125.08,124.62,112.97,59.90,34.66,30.99,30.63,22.37,21.28,17.78,17.58.

[0222] HRMS(ESI)m / z[M-BF4] + :calcd.599.3421,found 599.3418.

[0223] IR(film):ν max (cm -1 )3128,2964,1604,1537,1482,1444,1276,1194,1059,912,848,764,742.

[0224] Optical rotation:[α] D 25 =21.97(c=2.175,CHCl3).

[0225] 1H NMR(400 MHz,CDCl3)δ8.66(s,1H),7.53(t,J=7.7 Hz,1H),7.39–7.31(m,2H),7.30–7.25(m,1H),6.98(s,1H),6.90(s,1H),6.74(s,2H),6.27(dd,J=6.5,4.3 Hz,1H),3.21(ddd,J=17.0,7.1,4.5 Hz,1H),3.01(ddd,J=17.0,8.4,4.4 Hz,1H),2.72(ddt,J=12.9,8.4,4.4 Hz,1H),2.57–2.44(m,5H),2.39–2.30(m,1H),2.28–2.19(m,7H),2.10(dt,J=14.8,7.5 Hz,1H),1.12(t,J=7.5 Hz,3H),1.00(t,J=7.6 Hz,3H).

[0226] 13 C NMR(101 MHz,CDCl3)δ142.50,140.75,139.66,139.38,139.08,137.62,131.67,131.12,130.71,129.68,127.71,127.57,127.19,126.69,126.02,123.95,109.72,59.21,30.40,24.19,23.53,22.18,21.30,21.19,14.93,14.33.

[0227] HRMS(ESI)m / z[M-BF4] + :calcd.409.2638,found 409.2635.

[0228] IR(film):ν max (cm -1 )3119,2970,2935,1607,1537,1504,1465,1197,1058,914,843,730.

[0229] Optical rotation:[α] D 25 =69.60(c=1.760,CHCl3).

[0230] 1H NMR(400 MHz,CDCl3)δ8.73(s,1H),8.28(s,2H),8.06(s,1H),7.42–7.36(m,3H),7.36–7.29(m,3H),7.18(s,1H),5.98(dd,J=8.0,4.2 Hz,1H),3.18(ddd,J=17.2,8.3,4.9 Hz,1H),3.09(dt,J=17.1,5.5Hz,1H),2.67–2.49(m,5H).

[0231] 13 C NMR(101 MHz,CDCl3) 13 C NMR(101 MHz,cdcl3)δ140.10,138.52,136.00,135.03,134.13(q,J=34.8 Hz),130.25,129.54,129.51,128.07,127.22,127.05,126.11(d,J=4.0 Hz)126.04,124.43–124.14(m),122.22(q,J=273.5 Hz),121.29,109.44,60.35,30.17,22.28,22.17.

[0232] 19 F NMR(376 MHz,CDCl3)δ-62.96,-152.53.

[0233] HRMS(ESI)m / z[M-BF4] + :calcd.461.1447,found 461.1447.

[0234] IR(film):ν max (cm -1 )3069,2933,1617,1548,1499,1391,1356,1187,1142,1060,908,764,750,701.

[0235] Optical rotation:[α] D 25 =72.36(c=1.715,CHCl3).

[0236] 1H NMR(400 MHz,CDCl3)δ8.85(s,1H),7.98(t,J=1.7 Hz,1H),7.87(d,J=1.6 Hz,2H),7.73–7.65(m,4H),7.49–7.42(m,4H),7.41–7.35(m,5H),7.33(s,1H),7.32–7.26(m,3H),6.14(dd,J=7.1,4.2 Hz,1H),3.14(ddd,J=17.2,7.4,4.7 Hz,1H),3.04(ddd,J=17.1,7.4,4.6 Hz,1H),2.61(ddt,J=16.0,8.4,3.7Hz,1H),2.56–2.45(m,4H).

[0237] 13 C NMR(101 MHz,CDCl3)δ144.32,139.43,138.73,138.19,136.83,134.41,130.34,129.43,129.33,129.11,128.49,128.07,127.78,127.27,126.91,126.68,125.66,121.88,110.30,59.56,30.12,22.25,21.63.

[0238] HRMS(ESI)m / z[M-BF4] + :calcd.477.2325,found 477.2321.

[0239] IR(film):ν max (cm -1 )3136,3062,1596,1577,1499,1297,1205,1058,912,837,762,731,701.

[0240] Optical rotation:[α] D 25 =107.23(c=2.065,CHCl3).

[0241] 1H NMR(400 MHz,CDCl3)δ8.31(s,1H),7.40–7.30(m,4H),7.25–7.18(m,5H),7.11(s,1H),6.86(ddd,J=8.3,7.0,1.8 Hz,1H),5.86(dd,J=8.0,3.9 Hz,1H),3.19–3.08(m,1H),3.00(dt,J=17.1,5.3 Hz,1H),2.63–2.51(m,1H),2.46–2.37(m,4H).

[0242] 13 C NMR(101 MHz,CDCl3)δ151.45,139.06,138.45,136.39,131.93,130.85,129.53,129.47,127.57,126.87,126.38,126.26,125.03,120.30,120.25,118.57,111.11,59.91,30.67,22.12.

[0243] HRMS(ESI)m / z[M-BF4] + :calcd.341.1648,found 341.1646.

[0244] IR(film):ν max (cm -1 )3378,3139,3066,2929,1603,1545,1464,1351,1293,1208,1064,913,731.

[0245] Optical rotation:[α] D 25 =92.88(c=1.340,CHCl3).

[0246] 1H NMR(400 MHz,CDCl3)δ8.27(s,1H),7.38–7.29(m,5H),7.23(t,J=4.2 Hz,2H),7.16(dd,J=7.9,1.6 Hz,1H),7.10(s,1H),6.87(t,J=7.7 Hz,1H),5.83(dd,J=8.8,3.9 Hz,1H),3.18(ddd,J=16.9,9.3,4.6Hz,1H),3.04(dt,J=17.1,5.1 Hz,1H),2.58(dq,J=14.4,5.0 Hz,1H),2.55–2.42(m,4H),2.21(s,3H).

[0247] 13 C NMR(101 MHz,CDCl3)δ150.54,138.94,138.45,136.16,133.04,130.97,129.52,127.79,127.22,126.19,125.08,123.93,121.03,119.81,110.82,60.05,30.51,22.52,22.14,16.35.

[0248] HRMS(ESI)m / z[M-BF4] + :calcd.355.1805,found 355.1803.

[0249] IR(film):ν max (cm -1 )3408,3139,3064,2926,1601,1544,1489,1456,1300,1270,1205,1063,840,784,734,702.

[0250] Optical rotation:[α] D 25 =50.33(c=0.725,CHCl3).

[0251] 1H NMR(400 MHz,CDCl3)δ8.30(s,1H),7.39–7.31(m,3H),7.24(dd,J=7.7,1.9 Hz,3H),7.19(s,1H),7.13(s,1H),7.08(s,2H),5.85(dd,J=8.4,3.9 Hz,1H),3.16(ddd,J=17.0,8.8,4.6 Hz,1H),3.02(dt,J=17.2,5.2 Hz,1H),2.58(ddd,J=13.9,6.0,4.1 Hz,1H),2.51–2.40(m,4H),2.24(s,3H).

[0252] 13 C NMR(101 MHz,CDCl3)δ148.64,139.05,138.17,136.24,132.65,130.80,130.45,129.52,129.48,127.54,126.90,126.50,126.27,124.99,119.79,118.27,111.11,59.94,30.63,22.20,22.12,20.13.

[0253] HRMS(ESI)m / z[M-BF4] + :calcd.355.1805,found 355.1803.

[0254] IR(film):ν max (cm -1 )3365,3137,2928,1543,1516,1455,1295,1209,1062,823,734,702.

[0255] Optical rotation:[α] D 25 =34.76(c=1.125,CHCl3).

[0256] 1H NMR(400 MHz,CDCl3)δ8.26(s,1H),7.74(s,1H),7.41–7.32(m,3H),7.29–7.19(m,5H),7.12(s,1H),7.05(d,J=1.8 Hz,1H),6.72(dd,J=8.1,1.8 Hz,1H),5.86(dd,J=8.4,3.9 Hz,1H),3.17(ddd,J=17.0,8.9,4.5 Hz,1H),3.03(dt,J=17.2,5.2 Hz,1H),2.60(ddt,J=14.5,6.1,4.3 Hz,1H),2.54–2.44(m,4H),2.27(s,3H).

[0257] 13 C NMR(101 MHz,CDCl3)δ150.72,142.94,139.05,138.28,136.29,130.94,129.56,129.52,127.57,126.92,126.25,126.00,124.98,121.46,118.90,117.61,111.07,59.94,30.68,22.22,22.14,21.27.

[0258] HRMS(ESI)m / z[M-BF4] + :calcd.355.1805,found 355.1802.

[0259] IR(film):ν max (cm -1 )3379,3138,2926,1605,1545,1456,1297,1205,1134,1066,736,703.

[0260] Optical rotation:[α] D 25 =54.64(c=1.665,CHCl3).

[0261] 1H NMR(400 MHz,CDCl3)δ9.16(s,1H),7.46–7.30(m,5H),7.17(s,1H),7.01(s,1H),6.94(s,1H),6.84(s,2H),5.97(dd,J=7.1,4.2 Hz,1H),5.85(dd,J=9.5,3.7 Hz,1H),4.48(dd,J=12.0,9.6 Hz,1H),4.16(dd,J=12.1,3.6 Hz,1H),3.23–3.15(m,1H),3.03–2.92(m,1H),2.63–2.52(m,1H),2.51–2.37(m,5H),2.31–2.26(m,6H).

[0262] 13 C NMR(101 MHz,CDCl3)δ139.08,138.79,138.31,137.03,133.47,130.76,130.10,129.56,129.53,128.03,127.20,126.04,125.20,124.51,110.88,64.29,63.28,59.27,30.37,22.16,21.68,21.19.

[0263] HRMS(ESI)m / z[M-BF4] + :calcd.397.2274,found 397.2272.

[0264] IR(film):ν max (cm -1 )3132,2946,1695,1607,1544,1505,1343,1305,1203,1063,844,702.

[0265] Optical rotation:[α] D 25 =92.01(c=0.105,CHCl3).

[0266] 1H NMR(500 MHz,CDCl3)δ7.39–7.31(m,3H),7.05(s,1H),7.04(s,2H),7.01–6.97(m,2H),6.70(s,1H),5.93–5.86(m,1H),2.97(dt,J=16.8,4.6 Hz,1H),2.83(ddd,J=16.4,9.3,5.7 Hz,1H),2.61–2.53(m,2H),2.45(s,3H),2.39(s,3H),2.02(s,3H),1.98(s,3H).

[0267] 13 C NMR(126 MHz,CDCl3)δ140.01,139.44,135.52,135.35,132.91,132.61,129.78,129.64,129.56,129.08,128.29,125.89,123.21,123.07,108.97,59.09,31.00,21.82,21.12,20.82,17.91,17.82。

Claims

1. A compound as shown in Formula I, characterized in that, in, X is BF4 - or Cl - ; R 1 It is a C1-C6 alkyl, C1-C6 alkoxy or C6-C 14 aryl; R 2 For any one, two, or three Rs 2-1 Replacement C6-C 10 aryl or -CHR 2-2 R 2-3 ; R 2-1 Independently, one, two, or three Rs can be selected. 2-1-1 Substituted C1-C6 alkyl groups, optionally with one, two, or three R... 2-1-2 Substituted C1-C6 alkoxy groups, C6-C 10 aryl or hydroxyl groups; R 2-1-1 and R 2-1-2 Halogens are independent of each other; R 2-2 For C6-C 10 aryl; R 2-3 For any one, two, or three Rs 2-3-1 Substituted C1-C6 alkyl groups; R 2-3-1 Independently, it is a hydroxyl group; R 3 For any one, two, or three Rs 3-1 Replacement C6-C 10 aryl; R 3-1 It is a C1-C6 alkyl, C1-C6 alkoxy or C6-C 10 Aryl groups.

2. The compound of formula I as claimed in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) The C1-C6 alkyl group and the C1-C6 alkyl group of each of the substituted C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; (2) The C1-C6 alkoxy group and the substituted C1-C6 alkoxy group are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy. (3)R 1 In the context, the C6-C 14 The aryl group is independently phenyl or (4) Each of the C6-C 10 aryl and each of the substituted C6-C 10 C6-C in aryl 10 The aryl group is independently phenyl or naphthyl; and (5) The halogen is independently fluorine, chlorine, bromine or iodine.

3. The compound of formula I as described in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) X is BF4 - ; (2)R 1 It is a C1-C6 alkyl or C6-C 14 aryl; (3)R 2 For 1, 2 or 3 R 2-1 Replacement C6-C 10 Aryl groups, for example (4)R 2-1 Independently, one, two, or three Rs can be selected. 2-1-1 Substituted C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 aryl or hydroxyl groups; and (5)R 3-1 It is a C1-C6 alkyl or C1-C6 alkoxy group.

4. The compound of formula I as claimed in claim 1, characterized in that, It satisfies one or two of the following conditions: (1)R 1 It is an alkyl group of C1-C6; (2)R 2-1 It is an alkyl group that is independently C1-C6.

5. The compound of formula I as claimed in claim 1, characterized in that, It satisfies one or more of the following conditions: (1)R 1 Methyl, phenyl or (2)R 2 for (3)R 3 for 6. The compound of formula I as claimed in claim 1, characterized in that, The compound represented by Formula I is either Formula I-1 or Formula I-2. Among them, R 1 R 2-1 and R 3 The definition is as described in any one of claims 1-5.

7. The compound of formula I as claimed in claim 1, characterized in that, The compound represented by Formula I has any of the following structures.

8. A compound as shown in Formula II, characterized in that; Among them, R 1 R 2 and R 3 The definition is as described in any one of claims 1-7.

9. The compound of formula II as claimed in claim 8, characterized in that... ； The compound represented by Formula II has any of the following structures.

10. The use of a compound of Formula I as described in any one of claims 1-7 and / or a compound of Formula II as described in claims 8 or 9 as described in claims 9 as a catalyst in a silylated reaction.

11. The application as described in claim 10, characterized in that, The silylation reaction includes the following steps: in a solvent, in the presence of a catalyst and a base, compound A and compound B undergo a silylation reaction to prepare compound C; The catalyst is "cuprous chloride and the compound as shown in Formula I as described in claims 1-7" and / or "the compound as shown in Formula II as described in claims 8 or 9"; 12. The application as described in claim 11, characterized in that, It satisfies one or more of the following conditions; (1) The solvent is an ether solvent; (2) The base is an alkali metal salt of an alcohol; (3) The molar ratio of compound B to compound A is (1.2-1.8):1; (4) The molar ratio of cuprous chloride to the compound shown in Formula I is (0.8-1.2):1; (5) The molar ratio of the catalyst to compound A is (8-12):100; (6) The molar ratio of the base to compound A is (1.2-1.8):1; (7) The mass-to-volume ratio of compound A to the solvent is (0.012-0.018) g / mL; (8) The reaction time for the silanization reaction is 8-16 hours; (9) The reaction temperature of the silanization reaction is -5 to 5℃; (10) The silanization reaction further includes the following post-treatment steps: quenching and rotary drying; the quenching may be acetic acid quenching; and (11) The reactants for the silylation reaction are the solvent, the cuprous chloride, the compound as shown in Formula I, the base, the compound A and the compound B.

13. A single crystal of a compound as shown in Formula II-1, The single crystal belongs to the orthorhombic crystal system, space group P212121, and its unit cell parameters are: α=γ=β=90°, unit cell volume The number of asymmetric units within the unit cell is Z = 8, and the crystal density is 1.152 g / cm³. 3 .

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