Synthesis method of novel N, O, O-acetimidate ligand

Abstract

The invention discloses a green synthesis method for synthesizing a ligand containing N, O, O-tridentate acetimidate through a one-pot cascade reaction of three components of binaphthol, aryl diazonium salt and acetonitrile. Under the condition of 30-100 DEG C, aryl diazonium salt is used as an aryl source to react with acetonitrile and then react with phenolic hydroxyl groups of binaphthol to generate acetimidate substituted binaphthol. The method has the advantages of green reaction, no metal, simplicity in operation and no need of additional catalysts and additives; the raw materials are cheap, easy to obtain, wide in source and simple to prepare.

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis, and particularly relates to a method for synthesizing a novel N,O,O-acetimide ester ligand. Without using a catalyst or an additive, using aryl diazonium salt as an aryl source, acetonitrile as an imine source, and binaphthol as a substrate, the mono-substituted acetimidation reaction of binaphthol is achieved to obtain a binaphthol ligand substituted with N,O,O-tridentate acetimide ester. Background Art

[0002] Transition metal-catalyzed reactions are one of the important methods for the preparation of organic molecules, and the development of new ligands is the core research content in this field of research. (Jiang, Y. Jiang, Q. Zhu, G. Zhang, X. Tetrahedron Lett. 1997, 38, 215 - 218. Yamaishi, T. Ohnuki, M. Kiyooka, T. Masui, D. Sato, K. Yamaguchi, M. Tetrahedron: Asymmetry 2003, 14, 3275 - 3279. Wang, H. Wen, J. Zhang, X. Chem. Rev. 2021, 121, 7530 - 7567.) The development process of important reactions such as transition metal-catalyzed cyclopropanation, cross-coupling, allylation, and asymmetric hydrogenation is also the development process of ligands. A variety of chiral ligands containing phosphorus, nitrogen, and N-heterocyclic carbenes, etc., which are applicable to various metals such as palladium, rhodium, iridium, and cobalt, have been developed and have greatly promoted the development of other types of metal-catalyzed organic chemical reactions.(Ghorai, S. Chirke, S. S. Xu, W.-B. Chen, J.-F. Li, C. J. Am. Chem. Soc. 2019, 141, 11430 - 11434. Ghorai, S. Rehman, S. U. Xu, W.-B. Huang, W.-Y. Li, C. Org. Lett. 2020, 22, 3519 - 3523. Xu, W.-B. Ghorai, S. Huang, W. Li, C. ACS Catal. 2020. 10. 4491 - 4496. Huang, W.-Y. Lu, C.-H. Grohai, S. Li, B. Li, C. J. Am. Chem. Soc. 2020, 142, 15276 - 15281. Li, K. Li, C. Org. Lett. 2020, 22, 9456 - 9461. Chen, J.-F. Li, C. Org. Lett. 2020, 22, 4686 - 4691. Sun, M. Liu, M. Li, C. Chem. Eur. J. 2021, 27, 3457 - 3462. Liu, M. Zhao, H. Li, C. Chin. Chem. Lett. 2021, 32, 385 - 388. Xu, W.-B. Sun, M. Shu, M. Li, C. J. Am. Chem. Soc. 2021, 143, 8255 - 8260. Li, K. Wei, L. Sun, M. Li, B. Liu, M. Li, C. Angew. Chem. Int. Ed. 2021, 60, 20204 - 20209. Li, B. Liu, M. Rehman, S. U. Li, C. J. Am. Chem. Soc. 2022, 144, 2893 - 2898.)。

[0003] Multidentate ligands containing heteroatoms can coordinate well with metal atoms and have shown excellent coordination ability in coordination chemistry in recent years, attracting great interest. (Summary of the Symposium on the Development Strategy of Organic Chemistry in China in the 21st Century, Shanghai, 2001. John Boor, Jr. Ed., Sun Boqing, Zhang Yuba, Luan Yingjie, et al. Translators. Ziegler-Natta Catalysts and Polymerization [M]. Beijing: Chemical Industry Press, 1986. Huang Baotong, Shen Zhiquan, et al. Progress in Coordination Polymerization of Olefins and Diolefins [M]. Beijing: Science Press, 1998. Ernst, D. Bergmann, Pinchas. S. J. Org. Chem. 1950, 15, 1184 - 1190. Lantushenko, A. O. Meger, Y. V. Tverdokhleb, N. M. Yakovleva, Y. A. Eltsov, O. S. Evstigneev, M. P. J. Mol. Liq. 2021, 334, 116062. R. Nemec, V. N. D.Cryst.Growth Des.2022,22,5135-5142.Meher,N.Kumar.Kashyap,A.Geetharani,K.Chem.Asian J.2024,e202401085.) Their different active ligand sites, spatial structures, and electronic effects can well control the geometric configuration, catalytic activity, and selectivity of compounds. Commonly used ones include, for example, P,O-tridentate ligands, N,P-tridentate ligands, N,S-tridentate ligands, N,O-tridentate ligands, etc. These ligands can form stable conjugated rings with metal atoms. (Martin,F.Camelback.Hahn,T.M.Le.J.Am.Chem.Soc.1985,107,1455-1457.Bonomo,Raffaele.P.Conte,E.Guidi,Guido.De.Maccarrone,G.Rizzarelli,E.Vecchio,G.J.Chem.Soc.,Dalton Trans.1996,4345-4351.Spannenberg,A.Arndt,P.Kempe,R.Angew.Chem.Int.Ed.1998,37,832-835.Wang,C.Friedrich,S.Younkin,T.R.Li,R.T.Grubbs,R.H.Bansleben,D.A.Day,M.W.Organometallics 1998,17,3149-3151.Clerac,R.Cotton,F.A.Dunbar,K.R.Murillo,C.A.Pascual,I.Wang,X.Inorg.Chem.1999,38,2655-2657.Younkin,T.R.Connor,E.F.Henderson,J.I.Friedrich,S.K.Grubbs,R.H.Bansleben,D.A.Science 2000,288.1750-1751.Younkin,T.R.Connor,E.F.Henderson,J.I.Friedrich,S.k.Grubbs,R.H.Bansleben,D.A.Science 2000,287,460-462.Hicks,F.A.Jenkins,J.C.Brookhart,M.Organometallics,2003,22,3533-3545.Jenkins,J.C.Brookhart,M.Organometallics,2003,22,250-256.)Especially, it is mostly the case that nitrogen and oxygen heteroatoms act as coordination sites to form bonds with electron-deficient metal atoms through coordination. The synthesis of metal-organic compounds containing such ligands has gradually increased (Qian, Y. Zhao, W. Huang, J. Inorg. Chem. Commun. 2004, 7, 459 - 461. Sun, W. H. Zhang, W. Gao, T. Tang, X. Chen, L. Li, Y. Jin, X. J. Organomet. Chem. 2004, 43, 869 - 873. Jolanta, E. Micha, K. Lucjan, B. J. Chem. Soc., Dalton Trans. 2005, 2047 - 2050. Chen, H. Y. Lin, C. C. Tang, H. Y. Macromolecules 2006, 39, 3745 - 3752. Ejfler, J. Szafert, S. Mierzwicki, K. J. Chem. Soc., Dalton Trans. 2008, 6556 - 6562. Abell, J. P. Yamamoto, H. J. Am. Chem. Soc. 2008, 130, 10521 - 10523. Gou, S. Zhou, X. Wang, J. Liu, X. Feng. X. Tetrahedron 2008, 64, 2864 - 2870. Zhou, X. Liu, Y. Chang, L. Zhao, J. Shang, D. Liu, X. Lin, L. Feng, X. Adv. Synth. Catal. 2009, 351, 2567 - 2572. Zhou, X. Zhang, Q. Hui, Y. Chen, W. Jiang, J. Lin, L. Liu, X. Feng, X. Org. Lett. 2010, 12, 4296 - 4299. Suyama, K. Sakai, Y. Matsumoto, K. Saito, B. Katsuki, T. Angew. Chem. Int. Ed. 2010, 49, 797 - 799. Wen, Y.-Q. Hertzberg, R. Moberg, C. J. Org. Chem. 2014, 79, 6172 - 6178. Damkaci, F. Alawaed, A. Vik, E. Tetrahedron Lett. 2016, 57, 2197 - 2200. Wei, J. J. Song, W. B. Zhu, Y. F. Tetrahedron Lett. 2018, 74, 19 - 27. Jia, X. Peng, P. Cui, J. Xin, N. Huang, X. Asian J. Org. Chem.2018,7,1093 - 1100.Zhang,C.-W.;Hu,X.-Q.;Dai,Y.-H.;Yin,P.;Wang,C.;Duan,W.-L.ACS Catal.2022,12,193 - 199.).

[0004]

[0005] Using nitrogen and oxygen heteroatoms as ligand coordination sites Summary of the Invention

[0006] Without the need for a catalyst, additives, metals, acids, or bases, the present invention greenly and efficiently realizes the iminoesterification reaction of binaphthol under the conditions of only adding two reactants and a solvent.

[0007] The present invention uses aryl diazonium salts, which are simple to prepare and widely sourced, as raw materials, and acetonitrile as the imine source to achieve a three-component one-pot iminoesterification reaction with binaphthol.

[0008] A method for synthesizing an N,O,O-acetiminoester ligand, characterized in that: adding an aryl diazonium salt and a substrate in a solvent, using the aryl diazonium salt as the aryl source and the solvent as the imino group source, and under heating conditions, the acetiminoesterification reaction of the phenolic hydroxyl group can be realized to obtain an N,O,O-tridentate acetiminoester ligand.

[0009] The substrate is binaphthol, 2'-methoxy-[1,1'-binaphthalen]-2-ol, 2'-hydroxy-[1,1'-binaphthalen]-2-yl trifluoromethanesulfonate, 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalen]-2-ol, 5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalen]-2,2'-diol, 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol or R-binaphthol.

[0010] Taking the substrate as binaphthol as an example,

[0011] Among them, the reaction process is shown in the following reaction formula;

[0012]

[0013] Among them

[0014] R 1 represents a series of substituents at different positions such as the ortho, meta, and para positions of the benzene ring.

[0015] Among them R 1A substituent at one or more different positions such as the ortho, meta, and para positions of the benzene ring, the number of substituents being 1 - 5, preferably 1 - 2, and specifically being one or more of methyl, isopropyl, tert-butyl, ethynyl, benzyl, chlorine, bromine, and iodine.

[0016] The said reaction comprises the following steps:

[0017] Binaphthol and aryl diazonium tetrafluoroborate are successively added into a container, then nitrogen replacement is carried out three to five times, and then a solvent is added. It is stirred at 30 - 100 °C for 0.5 - 12 hours to obtain an N,O,O-tridentate iminoester-substituted binaphthol ligand (III) compound.

[0018] In the said reaction, the temperature is 40 - 100 °C, and the preferred reaction temperature is 60 - 90 °C.

[0019] In the said reaction, the solvent is any one or any combination of acetonitrile, 1,2-dichloroethane, cyclohexane, and n-hexane. The preferred solvent is acetonitrile, and the concentration of binaphthol in the solvent is 0.05 - 0.2 M, preferably the concentration of binaphthol in the solvent is 0.05 M.

[0020] In the said reaction, the molar ratio of the amount of binaphthol to the amount of aryl diazonium salt used is 1:0.8 - 1:2, and the preferred molar ratio of the amount of binaphthol to the amount of aryl diazonium salt used is 1:1 - 1.2.

[0021] The said reaction time is 0.5 - 12 hours, and the preferred reaction time is 2 hours.

[0022] The synthesized N,O,O-tridentate iminoester-substituted binaphthol ligand has a structure as shown in formula (Ⅲ)

[0023]

[0024] R 1 Preferably one or more of 4-methyl, 4-isopropyl, 4-tert-butyl, 4-ethynyl, 4-benzyl, 4-chloro, 4-bromine, 4-iodine, 3-methyl, 3-tert-butyl, 3-bromine, 3-iodine, 2-methyl, 2-benzyl, 2-iodine, 2,6-dimethyl, 3,5-dimethyl, 3,4-dimethyl, 3-iodo-4-methyl, 1-naphthalene, the number of substituents being 1 - 5, preferably 1 - 2.

[0025] As shown in the above reaction formula, in the present invention, without metal and catalyst, using binaphthol (I), aryl diazonium salt (II), and acetonitrile as both raw materials and solvents, a three-component one-pot reaction is achieved under certain temperature conditions to obtain a 2'-hydroxy-[1,1'-binaphthalene]-2-(E)-N-phenyl iminoester compound (Ⅲ)

[0026] In the present invention, in the reaction, the reaction solvent is any one or any combination of acetonitrile, n-hexane, cyclohexane, and 1,2-dichloroethane, and the preferred solvent is acetonitrile.

[0027] In the present invention, in the reaction, the molar ratio of the amount of binaphthol to the aryl diazonium salt is 1:0.8 - 1:2, and the preferred molar ratio of the amount used is 1:1.2.

[0028] In the present invention, in the reaction, the reaction time is 0.5 - 12 hours, and the preferred reaction time is 2 hours.

[0029] The advantages of the present invention are as follows:

[0030] The present invention realizes the acetylimidoesterification reaction of binaphthol greenly and efficiently under metal-free conditions without a catalyst and a promoter. All raw materials used in the present invention are industrial commodities, with cheap, easily available, wide sources, and simple accessibility; the reaction is green, the operation is simple, and no external catalyst or additive is required. Description of the Drawings

[0031] Figure 1 is the 1H NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 1

[0032] Figure 2 is the 13C NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 1

[0033] Figure 3 is the 1H NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(p-tolyl)acetimidate in Example 15 Figure 4 is the 13C NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(p-tolyl)acetimidate in Example 15 Figure 5 is the 1H NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(4-isopropylphenyl)acetimidate in Example 16

[0034] Figure 6 is the 13C NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(4-isopropylphenyl)acetimidate in Example 16

[0035] Figure 7 is the 1H NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(4-tert-butylphenyl)acetimidate in Example 17

[0036] Figure 813C NMR spectrum of the product of Example 17, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-tert-butylphenyl)acetimidate

[0037] Figure 9 1H NMR spectrum of the product of Example 18, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-ethynylphenyl)acetimidate

[0038] Figure 10 13C NMR spectrum of the product of Example 18, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-ethynylphenyl)acetimidate

[0039] Figure 11 1H NMR spectrum of the product of Example 19, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-benzylphenyl)acetimidate Figure 12 13C NMR spectrum of the product of Example 19, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-benzylphenyl)acetimidate Figure 13 1H NMR spectrum of the product of Example 20, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-chlorophenyl)acetimidate Figure 14 13C NMR spectrum of the product of Example 20, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-chlorophenyl)acetimidate Figure 15 1H NMR spectrum of the product of Example 21, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-bromophenyl)acetimidate Figure 16 13C NMR spectrum of the product of Example 21, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-bromophenyl)acetimidate Figure 17 1H NMR spectrum of the product of Example 22, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-iodophenyl)acetimidate Figure 18 13C NMR spectrum of the product of Example 22, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-iodophenyl)acetimidate Figure 19 1H NMR spectrum of the product of Example 23, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3-methylphenyl)acetimidate Figure 20 13C NMR spectrum of the product of Example 23, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3-methylphenyl)acetimidate Figure 21 1H NMR spectrum of the product of Example 24, 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3-tert-butylphenyl)acetimidate

[0040] Figure 22 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-tert-butylphenyl)acetimidate in Example 24.

[0041] Figure 23 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-chlorophenyl)acetimidate in Example 25. Figure 24 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-chlorophenyl)acetimidate in Example 25. Figure 25 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-bromophenyl)acetimidate in Example 26. Figure 26 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-bromophenyl)acetimidate in Example 26. Figure 27 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-iodophenyl)acetimidate in Example 27. Figure 28 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(3-iodophenyl)acetimidate in Example 27. Figure 29 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-methylphenyl)acetimidate in Example 28. Figure 30 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-methylphenyl)acetimidate in Example 28. Figure 31 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-benzylphenyl)acetimidate in Example 29. Figure 32 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-benzylphenyl)acetimidate in Example 29. Figure 33 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-iodophenyl)acetimidate in Example 30. Figure 34 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-iodophenyl)acetimidate in Example 30.

[0042] Figure 35 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2,6-dimethylphenyl)acetimidate in Example 31.

[0043] Figure 36It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(2,6-dimethylphenyl)acetimidate in Example 31.

[0044] Figure 37 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3,5-dimethylphenyl)acetimidate in Example 32.

[0045] Figure 38 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3,5-dimethylphenyl)acetimidate in Example 32.

[0046] Figure 39 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3,4-dimethylphenyl)acetimidate in Example 33.

[0047] Figure 40 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3,4-dimethylphenyl)acetimidate in Example 33.

[0048] Figure 41 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(2-iodo-4-methylphenyl)acetimidate in Example 34.

[0049] Figure 42 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(2-iodo-4-methylphenyl)acetimidate in Example 34.

[0050] Figure 43 It is the proton NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(naphthalen-1-yl)acetimidate in Example 35.

[0051] Figure 44 It is the carbon-13 NMR spectrum of the product 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(naphthalen-1-yl)acetimidate in Example 35.

[0052] Figure 45 It is the proton NMR spectrum of the product 2'-methoxy-[1,1'-binaphthalen]-2-yl (E)-N-phenylacetimidate in Example 36.

[0053] Figure 46 It is the carbon-13 NMR spectrum of the product 2'-methoxy-[1,1'-binaphthalen]-2-yl (E)-N-phenylacetimidate in Example 36.

[0054] Figure 47 It is the 1H NMR spectrum of the product 2'-(((trifluoromethyl)sulfonyl)oxy)-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 37.

[0055] Figure 48 It is the 13C NMR spectrum of the product 2'-(((trifluoromethyl)sulfonyl)oxy)-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 37.

[0056] Figure 49 It is the 1H NMR spectrum of the product 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 38.

[0057] Figure 50 It is the 13C NMR spectrum of the product 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 38.

[0058] Figure 51 It is the 1H NMR spectrum of the product 2'-hydroxy-5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 39.

[0059] Figure 52 It is the 13C NMR spectrum of the product 2'-hydroxy-5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalene]-2-yl (E)-N-phenylacetimidate in Example 39.

[0060] Figure 53 It is the 1H NMR spectrum of the product 7'-hydroxy-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7-yl (E)-N-phenylacetimidate in Example 40.

[0061] Figure 54 It is the 13C NMR spectrum of the product 7'-hydroxy-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7-yl (E)-N-phenylacetimidate in Example 40.

[0062] Figure 55 It is the liquid phase diagram of the RS-binaphthol product in the chiral retention experiment of Example 45.

[0063] Figure 56 It is the liquid phase diagram of the R-binaphthol product in the chiral retention experiment of Example 45. Detailed implementation manners

[0064] In combination with the following specific embodiments, the present invention will be further described in detail. The protection scope of the present invention is not limited to the following embodiments. Without departing from the spirit and scope of the inventive concept, the changes and advantages that can be conceived by those skilled in the art are included in the present invention, and the appended claims are used as the protection scope. The processes, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the specifically mentioned content below, are all common knowledge and well-known general knowledge in the art, and the present invention has no particular limiting content. The data given in the following embodiments include specific operations, reaction conditions, and products. The purity of the product is determined by nuclear magnetic resonance identification to determine the target.

[0065] Example 1: Synthesis of 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-phenylacetimidate

[0066]

[0067] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added, and then the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg) was added. After three nitrogen displacements, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white foamy solid (36.9 mg, 91%). Detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, the parameters of the obtained product are 1 HNMR(600MHz,CDCl3)δ8.10(d,J=8.9Hz,1H),7.97(dd,J=8.5,2.6Hz,2H),7.92(d,J=8.2Hz,1H),7.53-7.48(m,2H),7.44(d,J=8.8Hz,1H),7.37(t,J=7.4Hz,1H),7.35–7.32(m,1H),7.31–7.27(m,2H),7.26-7.23(m,3H),7.18(d,J=8.5Hz,1H),7.05(t,J=7.4Hz,1H),6.69(d,J=7.9Hz,2H),6.34(s,1H),1.72(s,3H). 1313C NMR (150 MHz, CDCl3) δ 163.55, 152.37, 150.31, 147.67, 134.00, 133.92, 132.10, 130.75, 130.21, 129.14, 129.02, 128.25, 128.08, 127.23, 126.69, 126.02, 125.91, 124.98, 124.05, 123.73, 123.52, 122.56, 120.98, 119.07, 115.63, 15.85. HRMS (ESI) m / z Calcd for C 28 H 22 NO2, [M+H] + : 404.1645, Found 404.1642. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0068] Example 2

[0069] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction temperature is 50 °C. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer, and the target product 3a (22.2 mg, yield 55%) is obtained, indicating that the target product can be obtained in a relatively high yield under the condition of 50 °C.

[0070] Example 3

[0071] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction temperature is 70 °C. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer, and the target product 3a (22.6 mg, yield 56%) is obtained, indicating that the target product can be obtained in a relatively high yield under the condition of 70 °C.

[0072] Example 4

[0073] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction temperature is 80 °C. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer, and the target product 3a (22.2 mg, yield 55%) is obtained, indicating that the target product can be obtained in a relatively high yield under the condition of 80 °C.

[0074] Example 5

[0075] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction temperature is 90 °C. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer. The target product 3a (20.2 mg, yield 50%) is obtained, indicating that the target product can be obtained in a relatively good yield under the condition of 90 °C.

[0076] Example 6

[0077] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that in the reaction, the amount of acetonitrile is changed to 10 equivalents (1 mmol, 52.2 μL), and 1,2-dichloroethane is used to replace acetonitrile as the reaction solvent. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer. The target product 3a is obtained in a trace yield, indicating that the yield of the target product is low under the condition of using 1,2-dichloroethane as the solvent.

[0078] Example 7

[0079] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that in the reaction, the amount of acetonitrile is changed to 10 equivalents (1 mmol, 52.2 μL), and n-hexane is used to replace acetonitrile as the reaction solvent. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer. The target product 3a (16.2 mg, yield 40%) is obtained, indicating that the target product can be obtained in a relatively good yield under the condition of using n-hexane as the solvent.

[0080] Example 8

[0081] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that in the reaction, the amount of acetonitrile is changed to 10 equivalents (1 mmol, 52.2 μL), and cyclohexane is used to replace acetonitrile as the reaction solvent. The reaction is stopped, and after the same post-treatment as above, the obtained target product is determined by a nuclear magnetic resonance spectrometer. The target product 3a (18.2 mg, yield 45%) is obtained, indicating that the target product can be obtained in a relatively good yield under the condition of using cyclohexane as the solvent.

[0082] Example 9

[0083] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that in the reaction, the ratio of 1a to 2a is 1:1. The reaction is stopped, and after the same post-treatment as above, the target product 3a (26.7 mg, yield 66%) is obtained, indicating that the target product can be obtained in a relatively good yield under the condition that the ratio of 1a to 2a is 1:1.

[0084] Example 10

[0085] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the ratio of 1a to 2a in the reaction is 1:1.1. The reaction was stopped, and the target product 3a (30.7 mg, yield 76%) was obtained after the same post-treatment as above, indicating that under the condition of a ratio of 1a to 2a of 1:1.1 in the reaction, the target product can be obtained in a relatively good yield.

[0086] Example 11

[0087] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the ratio of 1a to 2a in the reaction is 1:1.3. The reaction was stopped, and the target product 3a (33.5 mg, yield 83%) was obtained after the same post-treatment as above, indicating that under the condition of a ratio of 1a to 2a of 1:1.3 in the reaction, the target product can be obtained in a relatively good yield.

[0088] Example 12

[0089] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction time is 1 h. The reaction was stopped, and the target product 3a (34.7 mg, yield 83%) was obtained after the same post-treatment as above, indicating that under the condition of a reaction time of 1 h, a better target product can be obtained.

[0090] Example 13

[0091] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction time is 3 h. The reaction was stopped, and the target product 3a (32.3 mg, yield 80%) was obtained after the same post-treatment as above, indicating that under the condition of a reaction time of 3 h, a better target product can be obtained.

[0092] Example 14

[0093] The reaction steps and operating conditions are the same as those in Example 1. The difference from Example 1 is that the reaction is carried out under air conditions. The reaction was stopped, and the target product 3a (19.4 mg, yield 48%) was obtained after the same post-treatment as above, indicating that under an air atmosphere, a better target product can be obtained.

[0094] Example 15: Synthesis of (E)-N-(p-tolyl)acetimidoyl 2'-hydroxy-[1,1'-binaphthalene]-2-yl ester

[0095]

[0096] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 4-methylphenyl diazonium tetrafluoroborate (2b) (0.12 mmol, 24.7 mg). Replace the nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a colorless foamy solid (31.3 mg, 75%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a colorless foamy solid (33.8 mg, 81%). Detected by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR(600MHz,CDCl3)δ8.07(d,J=8.9Hz,1H),7.95(dd,J=8.5,3.2Hz,2H),7.89(d,J=8.1Hz,1H),7.50-7.45(m,2H),7.41(d,J=8.9Hz,1H),7.35(t,J=7.3Hz,1H),7.31(t,J=7.5Hz,1H),7.29–7.25(m,1H),7.22(d,J=8.5Hz,1H),7.16(d,J=8.4Hz,1H),7.05(d,J=8.1Hz,2H),6.57(d,J=8.2Hz,2H),6.38(s,1H),2.29(s,3H),1.71(s,3H). 13 C NMR(150MHz,CDCl3)δ163.65,152.46,150.37,145.04,134.02,133.94,133.11,132.09,130.71,130.16,129.60,129.15,128.24,128.08,127.20,126.66,125.98,125.93,124.99,124.17,123.49,122.59,120.86,119.20,115.76,20.92,15.84.HRMS(ESI)m / zCalcd for C 29 H 24 NO2,[M+H] + :418.1802,Found 418.1794. It shows that the target product with the highest yield can be obtained under the above conditions.

[0097] Example 16: Synthesis of (E)-N-(4-isopropylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0098]

[0099] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, the reaction substrate 4-isopropylphenyl diazonium tetrafluoroborate (2c) (0.12 mmol, 28.6 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow oily liquid (35.0 mg, 78%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a yellow oily liquid (38.9 mg, 87%) was obtained. The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as follows 1 H NMR(600MHz,CDCl3)δ8.06(d,J=8.9Hz,1H),7.96–7.92(m,2H),7.88(d,J=8.1Hz,1H),7.48-7.45(m,2H),7.40(d,J=8.9Hz,1H),7.36–7.33(m,1H),7.30(ddd,J=8.1,6.8,1.1Hz,1H),7.28–7.24(m,2H),7.20(d,J=8.7Hz,1H),7.15(d,J=8.4Hz,1H),7.09(d,J=8.3Hz,2H),6.59(d,J=8.3Hz,2H),6.43(s,1H),2.89–2.76(m,1H),1.72(s,3H),1.21(s,3H),1.20(s,3H). 13 C NMR(150MHz,CDCl3)δ163.62,152.47,150.41,145.21,144.24,134.04,133.95,132.09,130.69,130.15,129.15,128.23,128.08,127.19,126.95,126.66,125.97,125.94,125.00,124.17,123.49,122.64,120.86,119.22,115.79,33.61,24.21,15.92.HRMS(ESI)m / z Calcd for C 31 H28 NO2, [M+H] + : 446.2115, Found 446.2108. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0100] Example 17: Synthesis of 2'-Hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(4-tert-butylphenyl)acetimidate

[0101]

[0102] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) into a dry and clean Schlenk tube, then add the reaction substrate 4-tert-butylphenyl diazonium tetrafluoroborate (2d) (0.12 mmol, 29.7 mg), perform nitrogen displacement three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a colorless oily liquid (35.4 mg, 77%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a colorless oily liquid (43.3 mg, 94%). The parameters of the obtained product are detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as 1 H NMR (600 MHz, CDCl3) δ 8.10 (d, J = 8.9 Hz, 1H), 7.99 (dd, J = 8.5, 3.9 Hz, 2H), 7.93 (d, J = 8.1 Hz, 1H), 7.53–7.49 (m, 2H), 7.47 (d, J = 8.9 Hz, 1H), 7.41–7.37 (m, 1H), 7.36–7.30 (m, 4H), 7.27 (s, 1H), 7.22 (d, J = 8.4 Hz, 1H), 6.70–6.66 (m, 2H), 6.46 (s, 1H), 1.77 (s, 3H), 1.34 (s, 9H). 1313C NMR (150 MHz, CDCl3) δ 163.59, 152.47, 150.40, 146.49, 144.84, 134.04, 133.92, 132.07, 130.66, 130.14, 129.14, 128.22, 128.08, 127.17, 126.65, 125.95, 125.91, 125.84, 124.99, 124.16, 123.49, 122.63, 120.57, 119.21, 115.80, 34.34, 31.56, 15.91. HRMS (ESI) m / z Calcd for C 32 H 29 NO2, [M+H] + : 460.2271, Found 460.2266. It shows that the target product with the highest yield can be obtained under the above conditions.

[0103] Example 18: Synthesis of 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(4-ethynylphenyl)acetimidate

[0104]

[0105] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 4-ethynylphenyl diazonium tetrafluoroborate (2e) (0.12 mmol, 25.9 mg), displace with nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white oily liquid (11.6 mg, 27%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a white oily liquid (27.5 mg, 64%). Detected by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 11H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 1H), 7.98–7.94 (m, 2H), 7.90 (d, J = 8.0 Hz, 1H), 7.52–7.46 (m, 2H), 7.41 (d, J = 8.9 Hz, 1H), 7.39–7.37 (m, 2H), 7.35 (ddd, J = 8.0, 6.9, 1.2 Hz, 1H), 7.32 (ddd, J = 8.1, 6.8, 1.2 Hz, 1H), 7.29–7.23 (m, 2H), 7.16 (d, J = 8.4 Hz, 1H), 6.63 - 6.54 (m, 2H), 6.06 (s, 1H), 3.02 (s, 1H), 1.67 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 163.44, 152.18, 150.18, 148.30, 133.90, 133.87, 133.05, 132.16, 130.85, 130.33, 129.14, 128.30, 128.11, 127.34, 126.75, 126.14, 125.90, 124.96, 123.81, 123.57, 122.44, 121.08, 118.79, 117.28, 115.31, 83.79, 76.54, 15.89. HRMS (ESI) m / z Calcd for C 30 H 21 NO2, [M + H] + : 428.1645, Found 428.1642. It shows that the target product with the highest yield can be obtained under the above conditions.

[0106] Example 19: Synthesis of (E)-N-(4-benzylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0107]

[0108] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube. Subsequently, add the reaction substrate 4-benzylphenyl diazonium tetrafluoroborate (2f) (0.12 mmol, 33.8 mg). Replace the gas with nitrogen three times. Then, use a syringe to add the solvent CH3CN (2 mL). Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a yellow oily liquid (20.8 mg, 42%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a yellow oily liquid (37.3 mg, 76%). The obtained product is detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the product are 1 H NMR(600MHz,CDCl3)δ8.06(d,J=8.9Hz,1H),7.96–7.91(m,2H),7.88(d,J=8.1Hz,1H),7.49–7.44(m,2H),7.38(d,J=8.9Hz,1H),7.34(ddd,J=8.0,6.8,1.1Hz,1H),7.30(ddd,J=8.1,6.8,1.1Hz,1H),7.28–7.24(m,3H),7.22–7.17(m,2H),7.17–7.12(m,3H),7.05(d,J=8.3Hz,2H),6.62–6.55(m,2H),6.34(s,1H),3.91(s,2H),1.70(s,3H). 13 C NMR(150MHz,CDCl3)δ163.63,152.40,150.36,145.67,141.44,136.43,134.00,133.93,132.10,130.73,130.18,129.56,129.15,129.00,128.53,128.25,128.08,127.22,126.67,126.13,126.01,125.92,124.98,124.09,123.50,122.59,121.07,119.12,115.67,41.41,15.90.HRMS(ESI)m / z Calcd for C 35 H 27 NO2,[M+H] + :494.2115,Found 494.2110. It shows that the target product with the highest yield can be obtained under the above conditions.

[0109] Example 20: Synthesis of 2'-Hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(4-chlorophenyl)acetimidate

[0110]

[0111] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, 4-chlorophenyl diazonium tetrafluoroborate (2g) (0.12 mmol, 27.2 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, TLC thin-layer chromatography analysis showed that no reaction occurred. In addition, the reaction was stirred at 90 °C for 2 h, and the same post-treatment method was used for separation and purification to obtain a yellow viscous liquid (27.6 mg, 63%). The obtained product was detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the product were 1 1H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 1H), 7.95 (dd, J = 8.2, 6.4 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.48 (dd, J = 14.3, 8.0 Hz, 2H), 7.39 (d, J = 8.9 Hz, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.32 (t, J = 7.7 Hz, 1H), 7.26 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 8.5 Hz, 1H), 7.19 (d, J = 8.6 Hz, 2H), 7.14 (d, J = 8.4 Hz, 1H), 6.55 (d, J = 8.6 Hz, 2H), 6.08 (s, 1H), 1.66 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 163.80, 152.18, 150.19, 146.33, 133.91, 133.89, 132.17, 130.87, 130.34, 129.15, 129.09, 129.07, 128.31, 128.11, 127.35, 126.76, 126.14, 125.90, 124.97, 123.86, 123.59, 122.42, 122.36, 118.81, 115.38, 15.83. HRMS (ESI) m / z Calcd for C 28 H 20 ClNO2, [M + H] + : 438.1255, Found 438.1250. It shows that the target product with the highest yield can be obtained under the above conditions.

[0112] Example 21: Synthesis of (E)-N-(4-bromophenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0113]

[0114] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added, followed by the reaction substrate 4-bromophenyl diazonium tetrafluoroborate (2h) (0.12 mmol, 32.5 mg). The tube was purged with nitrogen three times, and then the solvent CH3CN (2 mL) was added using a syringe. The reaction was stirred at 60 °C for 2 h. After the reaction was completed, TLC thin-layer chromatography analysis showed that no reaction occurred. In addition, the reaction was stirred at 90 °C for 2 h, and the same post-treatment method was used to isolate and purify to obtain a yellow viscous liquid (28.9 mg, 60%). The obtained product was detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the product were 1 H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 1H), 7.95 (dd, J = 8.2, 6.4 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.51–7.44 (m, 2H), 7.39 (d, J = 8.9 Hz, 1H), 7.37–7.33 (m, 4H), 7.28–7.24 (m, 1H), 7.23 (d, J = 8.5 Hz, 1H), 7.14 (d, J = 8.4 Hz, 1H), 6.55 (dt, J = 8.6, 2.5 Hz, 2H), 6.08 (s, 1H), 1.66 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 163.80, 152.18, 150.19, 146.33, 133.91, 133.89, 132.17, 130.87, 130.34, 129.15, 129.09, 129.07, 128.31, 128.11, 127.35, 126.76, 126.14, 125.90, 124.97, 123.86, 123.59, 122.42, 122.36, 118.81, 115.38, 15.83. HRMS (ESI) m / z Calcd for C 28 H 20 BrNO2, [M + H] + : 482.0750, Found 482.0741. It shows that the target product with the highest yield can be obtained under the above conditions.

[0115] Example 22: Synthesis of 2'-hydroxy-[1,1'-binaphthyl]-2-yl (E)-N-(4-iodophenyl)acetimidate

[0116]

[0117] The reaction substrate binaphthol (1a) (0.1mmol, 28.6mg) was added to a dry and clean Shrek tube, followed by the reaction substrate 4-iodophenyldiazonium tetrafluoroborate (2i) (0.12mmol, 38.1mg), and nitrogen was replaced three times. Then, the solvent CH3CN (2mL) was added using a syringe, and the reaction was stirred at 60°C for 2h. After the reaction was completed, it was concentrated under reduced pressure and separated and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1-15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain an orange viscous liquid (20.9mg, 40%). In addition, the reaction was stirred at 90°C for 2h, and the same post-treatment method was used to separate and purify the orange viscous liquid (46.3mg, 88%). The parameters of the obtained product were detected by nuclear magnetic resonance and high-resolution mass spectrometry. 1 H NMR (600MHz, CDCl3) δ8.09(d,J=8.9Hz,1H),7.96(dd,J=8.5,2.8Hz,2H),7.90(d,J=8.1Hz,1H),7.56–7.52(m,2H),7.51–7.46(m,2H),7.40(d ,J=8.9Hz,1H),7.38–7.34(m,1H),7.34–7.31(m,1H),7.29–7.24(m,2H ),7.16(d,J=8.5Hz,1H),6.46–6.35(m,2H),6.03(s,1H),1.67(s,3H). 13 C NMR (150MHz, CDCl3) δ163.60,152.14,150.14,147.49,137.97,133.87,133.85,132.13,130.85,130.33,129.12,128.29,128 .10,127.33,126.75,126.12,125.87,124.95,123.80,123.57,123.26,122.40,118.76,115.32,87.38,15.81.HRMS(ESI)m / z Calcd for C 28 H 20 INO2,[M+H] + :530.0612,Found530.0606. This indicates that under the above conditions, the target product can be obtained with the highest yield.

[0118] Example 23: Synthesis of (E)-N-(3-methylphenyl)-2'-hydroxy-[1,1'-binaphthalene]-2-yl acetimidate

[0119]

[0120] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added, and then the reaction substrate 3-methylphenyl diazonium tetrafluoroborate (2j) (0.12 mmol, 24.7 mg) was added. The tube was purged with nitrogen three times, and then the solvent CH3CN (2 mL) was added using a syringe. The reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white foam solid (30.2 mg, 72%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a white foam solid (38.9 mg, 93%) was obtained after separation and purification. The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as follows 1 H NMR (600 MHz, CDCl3) δ 8.07 (d, J = 8.9 Hz, 1H), 7.95 (d, J = 8.7 Hz, 2H), 7.90 (d, J = 8.1 Hz, 1H), 7.50–7.45 (m, 2H), 7.42 (d, J = 8.9 Hz, 1H), 7.37–7.33 (m, 1H), 7.33–7.29 (m, 1H), 7.28–7.25 (m, 1H), 7.22 (d, J = 8.4 Hz, 1H), 7.16 (d, J = 8.4 Hz, 1H), 7.12 (t, J = 7.6 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), 6.46 (d, J = 8.1 Hz, 2H), 6.35 (s, 1H), 2.29 (s, 3H), 1.71 (s, 3H). 1313C NMR (150 MHz, CDCl3) δ 163.43, 152.42, 150.36, 147.59, 138.79, 134.02, 133.94, 132.10, 130.73, 130.18, 129.15, 128.84, 128.24, 128.08, 127.21, 126.68, 126.00, 125.94, 125.02, 124.51, 124.08, 123.50, 122.60, 121.64, 119.12, 117.98, 115.68, 77.37, 77.16, 76.95, 21.50, 15.88. HRMS (ESI) m / z Calcd for C 29 H 23 NO2, [M+H] + : 418.1802, Found 418.1794. It shows that the target product with the highest yield can be obtained under the above conditions.

[0121] Example 24: Synthesis of 2'-hydroxy-[1,1'-binaphthalen]-2-yl (E)-N-(3-tert-butylphenyl) acetimidate

[0122]

[0123] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) into a dry and clean Schlenk tube, then add the reaction substrate 3-tert-butylphenyl diazonium tetrafluoroborate (2k) (0.12 mmol, 29.7 mg), displace with nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain an orange viscous liquid (33.6 mg, 67%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain an orange viscous liquid (38.4 mg, 84%). Detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, the parameters of the obtained product are 11H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.7 Hz, 2H), 7.90 (d, J = 8.1 Hz, 1H), 7.51 (d, J = 8.9 Hz, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.41 (d, J = 8.9 Hz, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.33–7.30 (m, 1H), 7.30–7.26 (m, 1H), 7.23 (d, J = 8.4 Hz, 1H), 7.20–7.14 (m, 2H), 7.06 (d, J = 7.9 Hz, 1H), 6.70 (s, 1H), 6.47 (d, J = 7.8 Hz, 1H), 6.34 (s, 1H), 1.69 (s, 3H), 1.29 (s, 9H). 13 13C NMR (150 MHz, CDCl3) δ 163.39, 152.37, 15-- 2.20, 150.37, 147.38, 133.99, 133.91, 132.13, 130.76, 130.19, 129.17, 128.56, 128.26, 128.09, 127.22, 126.68, 126.00, 125.88, 125.00, 124.12, 123.53, 122.63, 120.68, 119.14, 118.31, 117.99, 115.84, 34.79, 31.44, 15.87. HRMS (ESI) m / z Calcd for C 32 H 29 NO2, [M + H] + : 460.2271, Found 460.2263. It shows that the target product with the highest yield can be obtained under the above conditions.

[0124] Example 25: Synthesis of (E)-N-(3-chlorophenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0125]

[0126] In a dry and clean Schlenk tube, the reaction substrate 1,1'-binaphthalene-2,2'-diol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, the reaction substrate 3-chlorobenzenediazonium tetrafluoroborate (2l) (0.12 mmol, 27.2 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow viscous liquid (24.0 mg, 55%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a yellow viscous liquid (31.3 mg, 72%) was obtained. The obtained product was detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the product were 1 H NMR(600MHz,CDCl3)δ8.08(d,J=8.9Hz,1H),7.99–7.92(m,2H),7.89(d,J=8.1Hz,1H),7.53–7.44(m,2H),7.40(d,J=8.9Hz,1H),7.37–7.30(m,2H),7.28–7.22(m,2H),7.17–7.11(m,2H),7.00(dd,J=8.0,1.1Hz,1H),6.60(t,J=1.9Hz,1H),6.51(dd,J=8.0,0.8Hz,1H),6.01(s,1H),1.67(s,3H). 13 C NMR(150MHz,CDCl3)δ163.81,152.16,150.14,149.04,134.48,133.88,132.18,130.87,130.38,130.07,129.16,128.31,128.13,127.36,126.77,126.16,125.92,124.97,123.79,123.60,122.42,121.21,119.31,118.77,115.25,15.90.HRMS(ESI)m / z Calcd for C 28 H 20 ClNO2,[M+H] + :438.1255,Found 438.1255. It shows that the target product with the highest yield can be obtained under the above conditions.

[0127] Example 26: Synthesis of (E)-N-(3-bromophenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0128]

[0129] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) into a dry and clean Schlenk tube, then add the reaction substrate 3-bromobenzenediazonium tetrafluoroborate (2m) (0.12 mmol, 32.5 mg). Conduct three nitrogen displacements, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a yellow viscous liquid (37.5 mg, 78%). In addition, this reaction is stirred at 90 °C for 2 h, and using the same post-treatment method, a yellow viscous liquid (41.0 mg, 85%) is separated and purified. Detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR (600 MHz, CDCl3) δ 8.09 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.7 Hz, 2H), 7.90 (d, J = 8.1 Hz, 1H), 7.51–7.46 (m, 2H), 7.41 (d, J = 8.9 Hz, 1H), 7.38–7.31 (m, 2H), 7.29–7.24 (m, 2H), 7.15 (d, J = 8.0 Hz, 2H), 7.09 (t, J = 7.9 Hz, 1H), 6.76 (d, J = 0.7 Hz, 1H), 6.60–6.53 (m, 1H), 5.99 (s, 1H), 1.68 (d, J = 0.7 Hz, 3H). 13 C NMR (150 MHz, CDCl3) δ 163.92, 152.13, 150.13, 149.17, 133.86, 132.17, 130.87, 130.38, 130.35, 129.15, 128.31, 128.‘13, 127.35, 126.77, 126.68, 126.16, 125.90, 124.97, 124.05, 123.75, 123.61, 122.54, 122.41, 119.77, 118.75, 115.24, 15.91. HRMS (ESI) m / z Calcd for C 28 H 20 BrNO2, [M + H] + : 482.0750, Found 482.0756. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0130] Example 27: Synthesis of (E)-N-(3-iodophenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0131]

[0132] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube. Subsequently, add the reaction substrate 3-iodobenzenediazonium tetrafluoroborate (2n) (0.12 mmol, 38.1 mg). Replace the air with nitrogen three times. Then, use a syringe to add the solvent CH3CN (2 mL), and stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow viscous liquid (39.2 mg, 78%). In addition, this reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a yellow viscous liquid (37.6 mg, 82%). Detected by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.7 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.48 (dd, J = 16.3, 8.2 Hz, 2H), 7.40 (d, J = 8.9 Hz, 1H), 7.37–7.30 (m, 3H), 7.25 (q, J = 8.1 Hz, 2H), 7.14 (d, J = 8.4 Hz, 1H), 6.97–6.90 (m, 2H), 6.58 (d, J = 8.0 Hz, 1H), 5.96 (s, 1H), 1.66 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 163.72, 152.13, 150.14, 149.07, 133.86, 132.65, 132.17, 130.86, 130.52, 130.37, 129.85, 129.15, 128.31, 128.13, 127.35, 126.76, 126.15, 125.91, 124.98, 123.74, 123.63, 122.41, 120.43, 118.74, 115.24, 94.28, 15.91. HRMS (ESI) m / z Calcd for C 28 H 20 INO2, [M + H] + : 530.0612, Found 530.0604. It shows that the target product with the highest yield can be obtained under the above conditions.

[0133] Example 28: Synthesis of (E)-N-(2-methylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-ylacetimidate

[0134]

[0135] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, the reaction substrate 2-methylphenyl diazonium tetrafluoroborate (2o) (0.12 mmol, 24.7 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow foamy solid (38.6 mg, 93%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a yellow foamy solid (40.6 mg, 97%) was obtained. The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as follows 1 H NMR (600 MHz, CDCl3) δ 8.09 (d, J = 8.9 Hz, 1H), 8.00–7.94 (m, 2H), 7.91 (d, J = 8.1 Hz, 1H), 7.51 (d, J = 8.9 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 8.9 Hz, 1H), 7.36 (t, J = 7.4 Hz, 1H), 7.33–7.26 (m, 2H), 7.23 (d, J = 8.5 Hz, 1H), 7.19 (d, J = 8.4 Hz, 1H), 7.11 (dd, J = 12.7, 7.4 Hz, 2H), 6.96 (t, J = 7.4 Hz, 1H), 6.56 (d, J = 7.8 Hz, 1H), 6.31 (s, 1H), 2.05 (s, 3H), 1.69 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 163.09, 152.42, 150.41, 146.17, 134.08, 133.98, 132.09, 130.60, 130.37, 130.17, 129.15, 128.61, 128.23, 128.09, 127.22, 126.67, 126.64, 126.02, 125.97, 125.00, 124.12, 123.79, 123.50, 122.60, 120.51, 119.14, 115.60, 17.81, 16.00. HRMS (ESI) m / z Calcd for C 29 H23 NO2, [M+H] + : 418.1802, Found 418.1797. It shows that the target product with the highest yield can be obtained under the above conditions.

[0136] Example 29: Synthesis of 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(2-benzylphenyl) acetimidate

[0137]

[0138] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) into a dry and clean Schlenk tube, then add the reaction substrate 2-benzylphenyl diazonium tetrafluoroborate (2p) (0.12 mmol, 33.8 mg). Replace the nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a yellow viscous liquid (29.1 mg, 59%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a yellow viscous liquid (40.9 mg, 83%). Detected by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR (600 MHz, CDCl3) δ 8.05 (d, J = 8.9 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.9 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.49–7.43 (m, 1H), 7.39 (d, J = 8.9 Hz, 1H), 7.34 (d, J = 8.9 Hz, 1H), 7.31–7.26 (m, 2H), 7.23–7.18 (m, 2H), 7.14 (t, J = 7.3 Hz, 2H), 7.10 (dd, J = 12.5, 6.0 Hz, 4H), 7.00 (d, J = 7.2 Hz, 2H), 6.99–6.94 (m, 1H), 6.42–6.35 (m, 1H), 6.01 (s, 1H), 3.70 (q, J = 14.9 Hz, 2H), 1.30 (s, 3H). 1313C NMR(150MHz,CDCl3)δ163.15,152.29,150.32,146.07,140.93,133.96,133.92,132.13,132.11,130.62,130.44,130.22,129.14,128.89,128.36,128.25,128.08,127.28,127.25,126.69,126.04,125.96,125.94,124.94,124.01,123.93,123.51,122.62,121.04,118.99,115.61,37.95,15.69.HRMS(ESI)m / z Calcd for C 35 H 27 NO2,[M+H][[ID=^5]] + :494.2115,Found 494.2109. It shows that the target product with the highest yield can be obtained under the above conditions.

[0139] Example 30: Synthesis of (E)-N-(2-iodophenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-ylacetimidate

[0140]

[0141] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 2-iodophenyl diazonium tetrafluoroborate (2q) (0.12 mmol, 38.Im g), displace with nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white solid, (23.0 mg, 43%), melting point: 171.9 - 173.7 °C. In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a white solid (33.1 mg, 63%). Detected by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 11H NMR (600 MHz, CDCl3) δ 8.11 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.95 (d, J = 8.9 Hz, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.75–7.71 (m, 2H), 7.50–7.46 (m, 1H), 7.40 (d, J = 8.9 Hz, 1H), 7.35 (ddd, J = 8.0, 6.8, 1.1 Hz, 1H), 7.31 (ddd, J = 8.1, 6.9, 1.0 Hz, 1H), 7.29–7.25 (m, 1H), 7.24–7.20 (m, 2H), 7.16 (d, J = 8.4 Hz, 1H), 6.73 (td, J = 7.7, 1.5 Hz, 1H), 6.62 (dd, J = 7.9, 1.5 Hz, 1H), 5.97 (s, 1H), 1.66 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 164.57, 152.20, 150.16, 149.36, 138.95, 134.03, 133.87, 132.28, 130.63, 130.27, 129.26, 129.13, 128.35, 128.10, 127.23, 126.74, 126.11, 125.91, 125.22, 125.05, 123.55, 123.47, 123.34, 121.10, 118.71, 115.16, 91.45, 16.60. HRMS (ESI) m / z Calcd for C 28 H 20 INO2, [M + H] + : 530.0612, Found 530.0609. It shows that the target product with the highest yield can be obtained under the above conditions.

[0142] Example 31: Synthesis of (E)-N-(2,6-dimethylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0143]

[0144] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, the reaction substrate 2,6-dimethylphenyl diazonium tetrafluoroborate (2r) (0.12 mmol, 26.4 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white foamy solid (42.2 mg, 98%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a white foamy solid (43.0 mg, 99%) was obtained. The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as 1 H NMR(600MHz,CDCl3)δ8.09(d,J=8.9Hz,1H),7.96(d,J=8.2Hz,1H),7.94(d,J=8.9Hz,1H),7.90(d,J=8.1Hz,1H),7.51(d,J=8.9Hz,1H),7.50–7.46(m,1H),7.38–7.33(m,2H),7.33–7.27(m,2H),7.23–7.18(m,2H),6.98(d,J=7.4Hz,1H),6.94(d,J=7.3Hz,1H),6.86(t,J=7.4Hz,1H),6.48(br.,1H),1.99(s,3H),1.93(s,3H),1.69(s,3H); 13 C NMR(150MHz,CDCl3)δ162.95,152.33,150.52,144.69,134.14,133.94,132.08,130.55,130.10,129.19,128.53,128.43,128.21,128.11,127.91,127.84,127.26,126.66,126.06,125.98,125.05,124.48,123.52,123.48,122.50,119.41,115.93,18.51,17.75,16.48.HRMS(ESI)m / z Calcd for C 30 H 25 NO2,[M+H] + :432.1958,Found432.1957. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0145] Example 32: Synthesis of (E)-N-(3,5-dimethylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-ylacetimidate

[0146]

[0147] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 3,5-dimethylphenyl diazonium tetrafluoroborate (2s) (0.12 mmol, 26.4 mg). Replace the nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow foamy solid (35.0 mg, 81%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to purify and obtain a yellow foamy solid (41.8 mg, 97%). Measured by nuclear magnetic resonance spectrometer and high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR (600 MHz, CDCl3) δ 8.06 (d, J = 8.9 Hz, 1H), 7.95 (d, J = 8.8 Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.50–7.45 (m, 2H), 7.41 (d, J = 8.9, 1H), 7.37–7.28 (m, 2H), 7.28–7.24 (m, 1H), 7.21 (d, J = 8.5 Hz, 1H), 7.15 (d, J = 8.4 Hz, 1H), 6.67 (s, 1H), 6.38 (s, 1H), 6.26 (s, 2H), 2.25 (s, 6H), 1.72 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 163.31, 152.47, 150.39, 147.51, 138.57, 134.04, 133.95, 132.08, 130.70, 130.14, 129.16, 128.23, 128.07, 127.17, 126.67, 125.96, 125.41, 125.06, 124.10, 123.48, 122.63, 119.16, 118.67, 115.73, 21.39, 15.90. HRMS (ESI) m / z Calcd for C 30 H 25 NO2, [M + H] + : 432.1958, Found 432.1954. It shows that the target product with the highest yield can be obtained under the above conditions.

[0148] Example 33: Synthesis of (E)-N-(3,4-dimethylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-ylacetimidate

[0149]

[0150] In a dry and clean Schlenk tube, the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) was added. Subsequently, the reaction substrate 3,4-dimethylphenyl diazonium tetrafluoroborate (2t) (0.12 mmol, 26.4 mg) was added. The tube was purged with nitrogen three times. Then, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 60 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a white foamy solid (31.6 mg, 73%). In addition, the reaction was stirred at 90 °C for 2 h, and using the same post-treatment method, a white foamy solid (37.6 mg, 87%) was obtained. The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as follows 1 H NMR(600MHz,CDCl3)δ8.07(d,J=8.9Hz,1H),7.95(d,J=8.7Hz,2H),7.90(d,J=8.1Hz,1H),7.50–7.45(m,2H),7.41(d,J=8.9Hz,1H),7.37–7.33(m,1H),7.30(t,J=7.7Hz,1H),7.28–7.25(m,1H),7.21(d,J=8.3Hz,1H),7.16(d,J=8.5Hz,1H),6.99(d,J=7.9Hz,1H),6.43(s,1H),6.41(dd,J=7.9,1.8Hz,1H),2.20(s,3H),2.19(s,3H),1.72(s,3H). 13 C NMR(150MHz,CDCl3)δ163.50,152.50,150.41,145.34,137.14,134.04,133.95,132.07,131.73,130.69,130.13,130.07,129.15,128.23,128.07,127.17,126.65,125.95,125.02,124.19,123.48,122.62,122.22,119.25,118.23,115.82,19.93,19.22,15.86.HRMS(ESI)m / z Calcd for C30 H 25 NO2,[M+H] + : 432.1958, Found 432.1954. It shows that the target product with the highest yield can be obtained under the above conditions.

[0151] Example 34: Synthesis of (E)-N-(2-iodo-4-methylphenyl)-2'-hydroxy-[1,1'-binaphthalen]-2-yl acetimidate

[0152]

[0153] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 2-iodo-4-methylphenyl diazonium tetrafluoroborate (2u) (0.12 mmol, 39.8 mg). Replace the nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow foamy solid (35.7 mg, 66%). In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a yellow foamy solid (42.5 mg, 78%). The parameters of the obtained product are detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as 1 H NMR(600MHz,CDCl3)δ8.10(d,J=8.9Hz,1H),7.96(d,J=8.2Hz,1H),7.95(d,J=8.9Hz,1H),7.89(d,J=8.1Hz,1H),7.72(d,J=8.9Hz,1H),7.58(d,J=1.0Hz,1H),7.48(ddd,J=8.1,6.8,1.1Hz,1H),7.40(d,J=8.9Hz,1H),7.35(ddd,J=8.0,6.8,1.1Hz,1H),7.30(ddd,J=8.1,6.8,1.1Hz,1H),7.27(ddd,J=6.7,4.7,1.3Hz,1H),7.21(d,J=8.5Hz,1H),7.16(d,J=8.4Hz,1H),7.03(dd,J=8.0,1.2Hz,1H),6.52(d,J=8.0Hz,1H),6.07(s,1H),2.24(s,3H),1.67(s,3H). 1313C NMR (150 MHz, CDCl3) δ 164.78, 152.27, 150.20, 146.77, 139.20, 134.95, 134.05, 133.88, 132.25, 130.60, 130.22, 130.02, 129.13, 128.33, 128.08, 127.19, 126.71, 126.06, 125.90, 125.05, 123.55, 123.53, 123.34, 120.69, 118.83, 115.29, 91.28, 20.32, 16.54. HRMS (ESI) m / z Calcd for C 29 H 22 INO2, [M+H] + : 544.0768, Found 544.0762. It shows that the target product with the highest yield can be obtained under the above conditions.

[0154] Example 35: Synthesis of 2'-hydroxy-[1,1'-binaphthalene]-2-yl (E)-N-(naphthalen-1-yl)acetimidate

[0155]

[0156] Add the reaction substrate binaphthol (1a) (0.1 mmol, 28.6 mg) to a dry and clean Schlenk tube, then add the reaction substrate 1-naphthyldiazonium tetrafluoroborate (2v) (0.12 mmol, 29.0 mg), displace nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 60 °C for 2 h. After the reaction is completed, analyze by TLC thin-layer chromatography, and only a trace amount of the target product can be obtained. In addition, the reaction is stirred at 90 °C for 2 h, and the same post-treatment method is used to separate and purify to obtain a yellow foamy solid (18.0 mg, 40%). Detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, the parameters of the obtained product are 11H NMR (600 MHz, CDCl3) δ 8.17 (d, J = 8.9 Hz, 1H), 8.01 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.1 Hz, 1H), 7.80 (d, J = 7.8 Hz, 1H), 7.69 (d, J = 8.9 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.56 (d, J = 8.2 Hz, 1H), 7.50 (ddd, J = 8.1, 6.8, 1.1 Hz, 1H), 7.48–7.41 (m, 3H), 7.40–7.35 (m, 2H), 7.34–7.30 (m, 2H), 7.30–7.26 (m, 1H), 7.24 (d, J = 8.5 Hz, 1H), 6.66 (d, J = 7.3 Hz, 1H), 6.24 (s, 1H), 1.68 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 163.95, 152.39, 150.45, 143.90, 134.25, 134.06, 134.00, 132.19, 130.90, 130.30, 129.21, 128.30, 128.14, 128.08, 127.31, 127.02, 126.77, 126.11, 126.00, 125.97, 125.64, 125.05, 124.09, 123.82, 123.57, 123.29, 122.51, 119.06, 115.95, 115.57, 16.12. HRMS (ESI) m / z Calcd for C 32 H 23 NO2, [M + H] + : 454.1802, Found 454.1797. It shows that the target product with the highest yield can be obtained under the above conditions.

[0157] Example 36: Synthesis of 2'-Methoxy-[1,1'-binaphthalen]-2-yl (E)-N-phenylacetimidate

[0158]

[0159] In a dry and clean Schlenk tube, add the reaction substrate 2'-methoxy-[1,1'-binaphthalene]-2-ol (1aa) (0.1 mmol, 30.0 mg). Subsequently, add the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg). Conduct three nitrogen displacements. Then, use a syringe to add the solvent CH3CN (2 mL), and stir the reaction at 90 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a white solid (28.1 mg, 67%). Melting point: 173.6 - 175.5 °C. Tested by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, the parameters of the obtained product are 1 H NMR (600 MHz, CDCl3) δ 8.04 (d, J = 9.0 Hz, 1H), 8.02 (d, J = 8.9 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.2 Hz, 1H), 7.61 (d, J = 8.9 Hz, 1H), 7.49 (d, J = 9.0 Hz, 1H), 7.44 (ddd, J = 8.1, 6.4, 1.5 Hz, 1H), 7.36 (ddd, J = 8.0, 6.7, 1.0 Hz, 1H), 7.34–7.30 (m, 2H), 7.30–7.26 (m, 1H), 7.24–7.20 (m, 1H), 7.14–7.08 (m, 2H), 6.95–6.89 (m, 1H), 6.23 (dd, J = 8.3, 1.0 Hz, 2H), 3.81 (s, 3H), 1.47 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 160.75, 155.16, 149.14, 148.55, 133.98, 133.95, 131.77, 129.91, 129.14, 129.05, 128.58, 128.23, 127.77, 126.53, 126.32, 126.30, 126.15, 125.32, 125.20, 123.70, 123.04, 122.84, 120.72, 118.76, 113.97, 57.02, 15.43. HRMS (ESI + ) m / z Calcd for C 29 H 23 NO2, [M + H] + : 418.1802, Found 418.1797. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0160] Example 37: Synthesis of 2'-(((trifluoromethyl)sulfonyl)oxy)-[1,1'-binaphthalen]-2-yl (E)-N-phenylacetimidate

[0161]

[0162] In a dry and clean Schlenk tube, the reaction substrate 2'-hydroxy-[1,1'-binaphthalen]-2-yl trifluoromethanesulfonate (1ab) (0.1 mmol, 41.8 mg) was added, followed by the addition of the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg). After three nitrogen displacements, the solvent CH3CN (2 mL) was added using a syringe, and the reaction was stirred at 90 °C for 2 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow viscous liquid (26.1 mg, 49%). The obtained product was detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the product were 1 H NMR (600 MHz, CDCl3) δ 8.10 (d, J = 9.1 Hz, 1H), 8.07 (d, J = 8.9 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.95 (d, J = 8.2 Hz, 1H), 7.62 (dd, J = 9.0, 2.8 Hz, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 8.6 Hz, 2H), 7.33–7.28 (m, 2H), 7.17 (d, J = 8.5 Hz, 1H), 7.06 (t, J = 7.8 Hz, 2H), 6.89 (t, J = 7.4 Hz, 1H), 6.06 (d, J = 7.5 Hz, 2H), 1.54 (s, 3H). 13 C NMR (150 MHz, CDCl3) δ 160.71, 149.46, 148.14, 145.58, 133.65, 133.41, 132.46, 131.56, 130.77, 130.61, 128.66, 128.34, 128.07, 127.61, 127.09, 126.81, 126.38, 125.90, 125.62, 123.04, 122.90, 121.88, 120.43, 119.46, 119.43, 117.30, 15.39. 19 F NMR (565 MHz, CDCl3) δ 3.24 (s). HRMS (ESI + ) m / z Calcd for C 29 H 20 F3NO4S, [M + H] +:536.1140, Found 536.1132. It shows that the target product with the highest yield can be obtained under the above conditions.

[0163] Example 38: Synthesis of 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalen]-2-yl-(E)-N-phenylacetimidate

[0164]

[0165] Add the reaction substrate 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalen]-2-ol (1ac) (0.1 mmol, 37.7 mg) to a dry and clean Schlenk tube, then add the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg). Purge with nitrogen three times, then add the solvent CH3CN (2 mL) using a syringe, and stir the reaction at 90 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here 5:1)) to obtain a yellow viscous liquid (33.8 mg, 68%). The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as 1 H NMR (600 MHz, CDCl3) δ 8.48 (dq, J = 4.8, 0.8 Hz, 1H), 8.04 (d, J = 8.9 Hz, 1H), 7.99 (d, J = 9.0 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.9 Hz, 1H), 7.48 (d, J = 9.0 Hz, 1H), 7.44 (ddd, J = 8.0, 6.7, 1.1 Hz, 1H), 7.41–7.3 (m, 3H), 7.34 (d, J = 8.4 Hz, 1H), 7.30–7.27 (m, 1H), 7.23 (ddd, J = 8.2, 6.8, 1.2 Hz, 1H), 7.09 (t, J = 7.8 Hz, 2H), 7.06 (dd, J = 7.0, 5.2 Hz, 1H), 6.94–6.89 (m, 2H), 6.23–6.16 (m, 2H), 5.30–5.23 (m, 2H), 1.48 (s, 3H). 1313C NMR (150 MHz, CDCl3) δ 160.70, 157.82, 153.81, 149.25, 148.70, 148.39, 136.60, 134.00, 133.97, 131.70, 129.96, 129.34, 129.03, 128.58, 128.17, 127.79, 126.59, 126.43, 126.34, 126.20, 125.32, 125.25, 123.95, 123.12, 122.86, 122.29, 121.09, 120.65, 119.41, 114.99, 71.84, 15.47. HRMS (ESI) m / z Calcd for C 34 H 26 N2O2, [M+H] + : 495.2067, Found 495.2062. It shows that the target product with the highest yield can be obtained under the above conditions.

[0166] Example 39: Synthesis of (E)-N-phenyl-2-(2'-hydroxy-5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalen]-2-yl)acetimidate

[0167]

[0168] Add the reaction substrate 5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalen]-2,2'-diol (1ad) (0.1 mmol, 37.7 mg) into a dry and clean Schlenk tube, then add the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg). Replace the air with nitrogen three times, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 90 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a yellow viscous liquid (29.6 mg, 72%). The obtained product was detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer, and the parameters of the obtained product were 29.6 mg, 72% yield. 11H NMR (600 MHz, CDCl3) δ 7.22–7.18 (m, 2H), 7.16 (d, J = 8.3 Hz, 1H), 7.01 (d, J = 8.3 Hz, 1H), 7.00–6.97 (m, 1H), 6.95 (d, J = 8.3 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), 6.66 (dd, J = 8.3, 1.0 Hz, 2H), 5.78 (s, 1H), 2.78 (dt, J = 28.2, 6.0 Hz, 4H), 2.47–2.36 (m, 2H), 2.14–2.05 (m, 2H), 1.76–1.63 (m, 8H), 1.68 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 163.68, 151.01, 149.23, 148.10, 138.25, 136.06, 135.46, 130.39, 129.76, 129.44, 129.28, 128.91, 124.11, 123.52, 121.16, 119.77, 114.67, 29.85, 29.52, 27.44, 26.99, 23.40, 23.32, 23.05, 22.85, 15.93. HRMS (ESI) m / z Calcd for C 28 H 29 NO2, [M + H] + : 412.2271, Found 412.2267. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0169] Example 40: Synthesis of 7'-hydroxy-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7-yl-(E)-N-phenylacetimidate

[0170]

[0171] Add the reaction substrate 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol (1ae) (0.1 mmol, 25.2 mg) into a dry and clean Schlenk tube, then add the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg), perform three nitrogen displacements, and then add the solvent CH3CN (2 mL) using a syringe. Stir the reaction at 90 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a colorless viscous liquid (11.8 mg, 32%). The parameters of the obtained product were detected by a nuclear magnetic resonance spectrometer and a high-resolution mass spectrometer as 11H NMR (600 MHz, CDCl3) δ 7.27 (t, J = 7.7 Hz, 1H), 7.23 (t, J = 7.8 Hz, 2H), 7.14 (d, J = 7.4 Hz, 1H), 7.08 (t, J = 7.7 Hz, 1H), 7.00 (dd, J = 17.0, 7.9 Hz, 2H), 6.87 (d, J = 7.5 Hz, 1H), 6.70 (d, J = 7.9 Hz, 2H), 4.64 (s, 1H), 3.09–3.00 (m, 4H), 2.43–2.25 (m, 4H), 1.33 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 161.35, 152.43, 148.95, 148.24, 146.55, 145.26, 138.54, 134.92, 128.92, 128.57, 123.29, 122.62, 122.32, 121.06, 117.65, 115.80, 58.73, 38.07, 37.87, 31.40, 31.30, 14.77. HRMS (ESI) m / z Calcd for C 25 H 23 NO2, [M + H] + : 370.1802, Found 370.1797. It shows that under the above conditions, the target product with the highest yield can be obtained.

[0172] Example 45: Chiral retention experiment

[0173]

[0174] Add the reaction substrate R - binaphthol (1a’) (0.1 mmol, 28.6 mg, 99% ee) into a dry and clean Schlenk tube, then add the reaction substrate phenyl diazonium tetrafluoroborate (2a) (0.12 mmol, 23.0 mg), conduct three nitrogen replacements, and then use a syringe to add the solvent CH3CN (2 mL). Stir the reaction at 90 °C for 2 h. After the reaction is completed, concentrate under reduced pressure and separate and purify by column chromatography (eluent: petroleum ether / ethyl acetate 1:1 - 15:1 plus 0.5% triethylamine, v / v, (here it is 5:1)) to obtain a white foamy solid (39.8 mg, 99%). The specific rotation of it is measured by a polarimeter as: [α] 25 D= 315.556 (c = 0.225, CH2Cl2 as the solvent), and its ee value was determined by high performance liquid chromatography to be 99%. The test conditions were as follows: the chiral column was AD-H, isopropanol / n-hexane = 10:90 as the eluent, the flow rate was 1 mL / min, the detector wavelength was 250 nm, the retention time of the main product was 6.834 minutes, and the retention time of the minor product was 6.004 minutes. It shows that under the action of the above conditions, the chiral structure of the target product can be well maintained, and product 3a’ can be used as a ligand in the catalysis of indole and unsaturated ketoesters.

Claims

1. A method for synthesizing an N,O,O-acetimidate ligand, characterized in that: Using aryl diazonium salts as the aryl source and solvents as the imino source, the acetoimidoesterification reaction of phenolic hydroxyl groups can be achieved under heating conditions to obtain N,O,O-tridentate acetoimidoester ligands.

2. The synthesis method according to claim 1, characterized in that: Using aryl diazonium salts as the aryl source and solvents as the imino source, under heating conditions, the N,O,O-tridentate acetoimidoester ligand (III) in the following reaction formula is obtained; the reaction process is shown in the following reaction formula; wherein R 1 represents one or more substituents at different positions such as ortho, meta, para positions on the benzene ring, the number of substituents is 1-5, preferably 1-2, and specifically it can be one or more of methyl, isopropyl, tert-butyl, ethynyl, benzyl, chlorine, bromine, iodine.

3. The synthesis method according to claim 2, characterized in that: The reaction includes the following steps: Add binaphthol and aryl diazonium salts into a container in sequence, then replace the nitrogen three to five times, and then add the solvent. Stir at 30-100 °C for 0.5-12 hours to obtain the N,O,O-tridentate acetoimidoester-substituted binaphthol ligand (III) compound.

4. The synthesis method according to claim 3, characterized in that: The temperature in the reaction is 40-100 °C, and the preferred reaction temperature is 60-90 °C.

5. The synthesis method according to claim 3, characterized in that: The solvent in the reaction is any one or any combination of acetonitrile, 1,2-dichloroethane, cyclohexane, and n-hexane. The preferred solvent is acetonitrile. The concentration of binaphthol in the solvent is 0.05-0.2 M, and the preferred concentration of binaphthol in the solvent is 0.05 M.

6. The synthesis method according to claim 3, characterized in that: The molar ratio of the amount of binaphthol to aryl diazonium salts used in the reaction is 1:0.8-1:2, and the preferred molar ratio of the amount of binaphthol to aryl diazonium salts used is 1:1-1.

2.

7. The synthesis method according to claim 3, characterized in that: The reaction time is 0.5-12 hours, and the preferred reaction time is 2 hours.

8. The synthesis method according to claim 3, characterized in that: The structure of the synthesized N,O,O-tridentate acetoimidoester-substituted binaphthol ligand is as shown in formula (Ⅲ) R 1 Preferably one or more of 4-methyl, 4-isopropyl, 4-tert-butyl, 4-ethynyl, 4-benzyl, 4-chloro, 4-bromo, 4-iodo, 3-methyl, 3-tert-butyl, 3-bromo, 3-iodo, 2-methyl, 2-benzyl, 2-iodo, 2,6-dimethyl, 3,5-dimethyl, 3,4-dimethyl, 3-iodo-4-methyl, 1-naphthyl; the number of substituents is 1-5, preferably 1-2.

9. The synthesis method according to claim 3, wherein: The binaphthol can also be replaced by 2'-methoxy-[1,1'-binaphthalene]-2-ol, 2'-hydroxy-[1,1'-binaphthalene]-2-yl trifluoromethanesulfonate, 2'-(pyridin-2-ylmethoxy)-[1,1'-binaphthalene]-2-ol, 5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthalene]-2,2'-diol, 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-6,6'-diol or R-binaphthol.

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