CN114478380B - Photo-redox catalytic N-aryl amine and cyclic ketoxime ester C (sp) 3 )-C(sp 3 ) Cross coupling process - Google Patents

Photo-redox catalytic N-aryl amine and cyclic ketoxime ester C (sp) 3 )-C(sp 3 ) Cross coupling process Download PDF

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CN114478380B
CN114478380B CN202210155323.2A CN202210155323A CN114478380B CN 114478380 B CN114478380 B CN 114478380B CN 202210155323 A CN202210155323 A CN 202210155323A CN 114478380 B CN114478380 B CN 114478380B
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CN114478380A (en
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李杨
周生运
李金恒
张鼎
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Nanchang Hangkong University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
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    • C07—ORGANIC CHEMISTRY
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    • C07—ORGANIC CHEMISTRY
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    • C07C253/00—Preparation of carboxylic acid nitriles
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    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
    • C07D217/16—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/18—Aralkyl radicals
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The application discloses a photo-oxidation reduction catalytic N-aryl amine and cyclic ketoxime ester C (sp 3 )‑C(sp 3 ) Cross coupling method. The method takes cyclic ketoxime ester as a cyanoalkylating reagent to realize C (sp) of N-aryl amine and cyclic ketoxime ester under the condition of no metal catalysis 3 )‑C(sp 3 ) The cross-coupling reactions, in which various N-aryl amines and cyclic ketoxime esters are converted into the corresponding target compounds in good to excellent yields under mild conditions, have a wide range of reaction substrate adaptations. The synthesis strategy can be applied to structural modification of d-aminocarbonyl compounds and short peptide compounds. The catalytic reaction condition is mild and simple, the reaction can be smoothly carried out at room temperature by taking 3CzClIPN as a catalyst, the reaction controllability is high, the cost is low, the high regioselectivity can be obtained without using a metal catalyst, alkali and/or other ligands, and the method is suitable for large-scale production.

Description

Photo-redox catalytic N-aryl amine and cyclic ketoxime ester C (sp) 3 )-C(sp 3 ) Cross coupling process
Technical Field
The application belongs to the technical field of organic synthesis methodologies, and in particular relates to a method for catalyzing N-aryl amine and cyclic ketoxime ester C (sp 3 )-C(sp 3 ) Cross coupling method.
Background
Functional amine compounds are considered to be important building blocks, widely present in drug molecules and natural product structures. General synthetic strategies for preparing and/or modifying such compounds due to their abundant chemical and biological activitiesHas attracted more and more attention. In the reported processes, alkylation of N-aromatic amines is one of the most efficient routes to nitrogen-containing organic compounds, which introduces C (sp 3 ) In part to alter the spatial conformation and increase the lipophilicity and hydrophilicity of the drug compound. Typical methods of N-arylamine alkylation rely mainly on CDC (cross-dehydrogenation coupling) reactions, although significant progress has been made in this regard, there are considerable limitations: (1) Most processes rely heavily on activated alkyl C (sp 3 ) Substrates whose H bonds are adjacent to heteroatoms (e.g. O, S and N) or electron withdrawing groups (e.g.nitriles, esters, ketones and amides). (2) Superstoichiometric oxidants and high temperatures are often required, resulting in poor chemoselectivity and atomic economy. Thus, mild and sustainable synthetic strategies were developed to achieve challenging C (sp 3 )-C(sp 3 ) Cross-coupling is still very desirable.
Visible light photocatalysis, due to its environmental friendliness and sustainability, has been developed as a powerful tool for organic conversion and has recently been applied to the alkylation of N-aromatic amines. In 2017, the Yu group of topics reported a novel visible light driven palladium catalyzed free radical alkylation of N-aryl amines with alkyl bromides, various tertiary, secondary and primary unactivated alkyl bromides were constructed under the simple conditions described to yield quaternary carbon centers (Angew.Chem., int.Ed.,2017, 56, 15683-15687). After a while, cong group developed photooxidative reductive decarboxylation alkylation of visible light N-aryl amines with N- (acyloxy) phthalimides using erythrosine B sensitized TiO 2 As photocatalysts (org.lett., 2018, 20, 3225-3228). The Zhang group of topics reported similar decarboxylation alkylation reactions by photoactivated electron donor-acceptor (EDA) complexes (org.chem. Front.,2021,8, 2473-2479). Furthermore, katritzky salts have also proven to be effective alkylation precursors for use in the visible light-promoted alkylation of N-aromatic amines (org. Chem. Front.,2019,6, 3902-3905; org. Lett.,2020, 22, 7290-7294). While these methods provide an effective method of alkylating N-aryl amines, they have focused primarily on these three sources of alkyl radicals, especially the distally substituted alkyl radicals, remain very highIs rare.
Recently, cyclic ketoxime esters having redox activity have been intensively explored as radical precursors by activation of c—c bonds under transition metal or photo-redox catalysis. 2021, gong, lu and colleagues developed a direct C-H cyanoalkylation of glycine derivatives with cyclobutanone oxime esters, the key to this conversion being the binding of Fe (NTf) 2 ) 2 And pyridine-oxazoline ligands as an effective catalytic system. Furthermore, the 2-aminocarbonyl moiety is essential for the chelation between the catalyst system and the glycine derivative (ACS catalyst, 2021, 11, 4288-4293). In light of the above work, the inventors contemplate whether it is possible to achieve free radical coupling of an N-aryl amine and a cyclic ketoxime ester under photoredox conditions.
Based on the previous assumptions combined with extensive experimental research, in the present application, a novel metal-free catalyzed C (sp 3 )-C(sp 3 ) Cross-coupling reactions involving direct C (sp 3 ) -H functionalization, various N-aryl amines and cyclic ketoxime esters are converted into the corresponding target compounds in good to excellent yields under mild conditions. The reaction proceeds by the sequence of imino radical formation, c—c bond cleavage to give cyanoalkyl radicals, single electron transfer to form nitrogen radical cations, deprotonation and radical-radical coupling.
Disclosure of Invention
The application aims to enrich the synthetic strategy of alkylated N-aryl amine compounds in the prior art, takes cyclic ketoxime ester as a cyanoalkylating reagent, and realizes C (sp 3 )-C(sp 3 ) Cross-coupling reactions, various N-aryl amines and cyclic ketoxime esters are converted to the corresponding target compounds in good to excellent yields under mild conditions.
According to the application, the photo-redox catalysis N-aryl amine and cyclic ketoxime ester C (sp 3 )-C(sp 3 ) A cross-coupling method comprising the steps of:
sequentially adding an N-arylamine compound shown in a formula 1, a cyclic ketoxime ester compound shown in a formula 2, a photocatalyst and an organic solvent into a reactor, then placing the reactor under room temperature and illumination for stirring reaction under the condition of protective atmosphere, and obtaining a target product shown in a formula 3 after the reaction is completed; the reaction formula is as follows:
in the above-mentioned reaction scheme, the reaction mixture,represents substituted or unsubstituted C 6-20 An aryl group; wherein the substituents are selected from halogen (preferably F, cl, br, I), C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 A haloalkyl group;
R 1 selected from hydrogen, C 1-6 Alkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 An alkyl group;
R 2 selected from C 1-6 Alkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 Alkyl, -C (O) OR 6 、-C(O)R 7 、-C(O)NR 8 R 9 ；
Wherein R is 6 、R 7 Selected from C 1-6 Alkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 An alkyl group;
R 8 ，R 9 independently of one another selected from C 1-6 Alkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 Alkyl, C substituted by R 1-6 Alkyl, wherein R' is selected from C 1-6 Alkoxy, C 1-6 Alkylthio, -C (O) OR 6 、-C(O)R 7 And/or R 8 ，R 9 Are connected to each other and to the connection R 8 ，R 9 Together form a substituted OR unsubstituted four-to seven-membered ring structure, wherein the substituents are-C (O) OR 6 、-C(O)R 7 ；
And/or R 1 ，R 2 Is connected with each other, and the N-arylamine compound shown in the formula 1 has the following formula1' of the structure shown in the specification:the target product represented by formula 3 has a structure represented by the following formula 3': />Wherein R' is selected from halogen (preferably F, cl, br, I), C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 A haloalkyl group;
R 3 selected from hydrogen, halogen (preferably F, cl, br, I), C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Haloalkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 An alkyl group;
x is selected from O, S, N or C, R when X is O, S 4 ，R 5 Absence of; when X is N, R 4 ，R 5 One is absent; when X is C, R 4 ，R 5 Presence;
R 4 ，R 5 independently of one another selected from hydrogen, C 1-6 Alkyl, C 6-20 Aryl, C 6-20 aryl-C 1-6 Alkyl, -C (O) OR 6 、-C(O)R 7 ；
n is an integer selected from 1, 2, 3 or 4;
ar is selected from substituted or unsubstituted C 6-20 Aryl, wherein the substituents are halogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 A haloalkyl group.
As C in any of the foregoing aspects of the application 1-6 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-hexyl.
As C in any of the foregoing aspects of the application 6-20 Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl and the like.
As C in any of the foregoing aspects of the application 1-6 Examples of haloalkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-propyl substituted with one or more of F, cl, br, IButyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like, specifically such as trifluoromethyl, difluoromethyl, monofluoromethyl, trichloromethyl, dichloromethyl, monofluorodichloromethyl, chlorodifluoromethyl, and the like.
As C in any of the foregoing aspects of the application 1-6 Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy and the like.
As C in any of the foregoing aspects of the application 6-20 aryl-C 1-6 Examples of alkyl groups include benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.
As C in any of the foregoing aspects of the application 1-6 Examples of alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, n-hexylthio and the like.
Preferably, the method comprises the steps of,represents a substituted or unsubstituted phenyl or naphthyl group; wherein the substituents are selected from F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, trifluoromethyl;
R 1 selected from hydrogen, methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl;
R 2 selected from methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl, -C (O) OR 6 、-C(O)R 7 、-C(O)NR 8 R9；
Wherein R is 6 、R 7 Selected from methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl;
R 8 ，R 9 independently of one another, selected from methyl, ethyl, tert-butyl, phenyl, naphthyl, benzyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl OR isopentyl substituted with R ', where R' is selected from methoxy, ethoxy, tert-butoxy, methylthio, ethylthio, -C (O) OR 6 、-C(O)R 7 And/or R 8 ，R 9 Are connected to each other and to the connection R 8 ，R 9 Together form a substituted OR unsubstituted tetrahydropyrrole structure, wherein the substituents are-C (O) OR 6 、-C(O)R 7 ；
And/or R 1 ，R 2 The N-arylamine compounds represented by formula 1 at this time have the structure represented by the following formula 1', being linked to each other:the target product represented by formula 3 has a structure represented by the following formula 3': />Wherein R' is selected from F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, trifluoromethyl;
R 3 selected from hydrogen, F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, phenyl, naphthyl, benzyl;
x is selected from O, S, N or C, R when X is O, S 4 ，R 5 Absence of; when X is N, R 4 ，R 5 One is absent; when X is C, R 4 ，R 5 Presence;
R 4 ，R 5 independently of one another, from the group consisting of hydrogen, methyl, ethyl, n-propyl, phenyl, naphthyl, benzyl, -C (O) OR 6 、-C(O)R 7 ；
n is an integer selected from 1, 2, 3 or 4;
ar is selected from substituted or unsubstituted phenyl or naphthyl, wherein the substituents are halogen, F, cl, br, I, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl.
Most preferably, the first and second regions are,represents a substituted or unsubstituted phenyl group, an unsubstituted naphthyl group; wherein the substituents are selected from F, cl, br, methyl, methoxy, trifluoromethyl;
R 1 selected from hydrogen;
R 2 selected from phenyl, -C (O) OR 6 、-C(O)R 7 、-C(O)NR 8 R 9 ；
Wherein R is 6 、R 7 Selected from methyl, ethyl, t-butyl, phenyl;
R 8 ，R 9 independently of one another, selected from methyl, ethyl, n-propyl, isobutyl OR isopentyl substituted by R ', where R' is selected from methylthio, -C (O) OR 6 And/or R 8 ，R 9 Are connected to each other and to the connection R 8 ，R 9 Together form a substituted OR unsubstituted tetrahydropyrrole structure, wherein the substituents are-C (O) OR 6 ；
And/or R 1 ，R 2 The N-arylamine compounds represented by formula 1 at this time have the structure represented by the following formula 1', being linked to each other:the target product represented by formula 3 has a structure represented by the following formula 3': />Wherein R' is selected from F, cl, br, methyl, methoxy, trifluoromethyl;
R 3 selected from hydrogen, methyl, phenyl;
x is selected from O, N or C, when X is O, R 4 ，R 5 Absence of; when X is N, R 4 ，R 5 One is absent; when X is C, R 4 ，R 5 Presence;
R 4 ，R 5 independently of one another, from the group consisting of hydrogen, methyl, ethyl, n-propyl, phenyl, -C (O) OR 6 ；
n is an integer selected from 1, 2 and 3;
ar is selected from trifluoromethyl substituted phenyl.
The method according to the application, wherein the photocatalyst is 3CzClIPN, fac-Ir (ppy) 3 ，Ru(bpy) 3 Cl 2 ，Eosin Y，[Acr][MesClO 4 ]Any one or a mixture of a plurality of rhodamine B and methylene blue; preferably, the photocatalyst is 3CzClIPN. Wherein the CAS number of the 3CzClIPN is 1469704-61-7, and the structural formula is as follows:
the method according to the application, wherein the organic solvent is selected from any one or a mixture of a plurality of acetonitrile, dichloroethane, methanol and DMSO; preferably, the organic solvent is selected from acetonitrile.
The method according to the application, wherein the protective atmosphere is an argon atmosphere or a nitrogen atmosphere, preferably an argon atmosphere.
The method according to the application as described above, wherein said illumination is preferably provided by a 5W LED blue light lamp.
According to the method of the application, the molar ratio of the N-arylamine compound shown in the formula 1, the cyclic ketoxime ester compound shown in the formula 2 and the photocatalyst is 1:1-3:0.01-0.1, preferably 1:1.2-1.5:0.03-0.05, and most preferably 1:1.2:0.03.
The method according to the present application, wherein the reaction time of the stirring reaction is 4 to 48 hours, preferably 8 to 36 hours, more preferably 12 to 24 hours, and most preferably 12 hours.
The method according to the application, wherein the post-treatment operation is as follows: the reaction solution was filtered, concentrated under reduced pressure, and the residue was separated by silica gel column chromatography to obtain the objective product represented by formula 3.
The method of the application has the following beneficial effects:
1. the application reports that the C (sp) of N-aryl amine and cyclic ketoxime ester is realized under the condition of no metal catalysis by taking the cyclic ketoxime ester as a cyanoalkylating reagent for the first time 3 )-C(sp 3 ) The cross coupling reaction, various N-aryl amine and cyclic ketoxime ester are converted into corresponding target compounds with good to excellent yield, has wide reaction substrate adaptation range, and can be applied to d-aminocarbonyl compounds and short reaction productsStructural modification of peptide compounds.
2. The catalytic reaction condition of the application is mild and simple, the 3CzClIPN can be smoothly carried out at room temperature as a catalyst, the reaction controllability is high, the cost is low, the high regioselectivity can be obtained without using a metal catalyst, alkali and/or other ligands, and the application is suitable for the scale-up production.
Detailed Description
The present application will be described in further detail with reference to specific examples. In the following, unless otherwise indicated, all procedures used are routine in the art and reagents used are commercially available in conventional manner and/or are prepared according to known organic synthetic methods.
Examples 1 to 16 reaction condition optimization experiments
The effect on the yield of the target product 3aa under different catalytic reaction conditions is explored by taking N-phenyl tetrahydroisoquinoline shown in a formula 1a and a cyclobutanonoxime ester compound shown in a formula 2a as raw materials, and the result is shown in a table 1, wherein the reaction formula is as follows:
table 1:
taking example 1 as an example, a typical reaction procedure is as follows:
n-phenyltetrahydroisoquinoline (0.2 mmol,41.8 mg) represented by formula 1a, a cyclobutanonoxime compound (1.2 equiv.,55.0 mg) represented by formula 2a, 3CzClIPN (3 mol%,4.7 mg) and MeCN (2.0 mL) were sequentially added to a Schlenk reactor, and then the reactor was stirred at room temperature under the protection of argon, and the reaction was completed as monitored by TLC and/or GC-MS by exposing the reactor to 5W blue LED to stirring at room temperature(about 12 hours), the reaction solution was filtered, concentrated under reduced pressure, and the residue was separated by silica gel column chromatography (n-hexane/ethyl acetate as an eluting solvent) to give 47.5mg of the objective product represented by formula 3aa in 86% yield. A yellow oily liquid is used for the preparation of the liquid, 1 H NMR(500MHz，CDCl 3 )δ7.23(t，J＝7.5Hz，2H)，7.16(d，J＝6.5Hz，2H)，7.11(d，J＝6.5Hz，2H)，6.88(d，J＝8.0Hz，2H)，6.76(d，J＝7.5Hz，1H)，4.67(t，J＝6.5Hz，1H)，3.66-3.57(m，2H)，3.02-2.96(m，1H)，2.76(d，J＝16Hz，1H)，2.33(t，J＝7.0Hz，2H)，2.09-2.04(m，1H)，1.93-1.83(m，2H)，1.80-1.75(m，1H)； 13 C NMR(126MHz，CDCl 3 )δ149.6，137.9，134.9，129.3，128.8，127.0，126.7，126.0，119.5，118.0，114.8，58.3，42.0，35.5，26.5，22.8，17.1；LRMS(EI，70eV)m/z(％)：276(M + ，4)，193(5)，208(100)，165(3)；HRMS m/z(ESI)calcd for C 19 H 20 N 2 [M+H] + 277.1699，found 277.1694。
based on the best catalytic reaction conditions obtained, the inventors have further explored the substrate suitability of the starting materials for the different substituents under the best reaction conditions of example 1, with the following results:
structural characterization of the product:
3ba: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.17-7.13(m，2H)，7.10(t，J＝3.0Hz，1H)，7.07(d，J＝7.0Hz，1H)，7.02(d，J＝8.0Hz，2H)，6.80(t，J＝4.0Hz，2H)，4.61-4.58(m，1H)，3.62-3.52(m，2H)，2.97-2.90(m，1H)，2.72-2.67(m，1H)，2.30(t，J＝8.5Hz，2H)，2.23(d，J＝3.5Hz，3H)，2.06-2.00(m，1H)，1.90-1.73(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ147.6，138.0，134.8，129.7，128.8，127.6，127.0，126.5，125.9，119.5，115.6，58.3，42.3，35.4，26.1，22.7，20.2，16.0；LRMS(EI，70eV)m/z(％)：290(M + ，3)，115(17)，222(100)，91(30)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 [M+H] + 291.1856，found 291.1860。
3ca: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.18-7.12(m，3H)，7.08(d，J＝7.5Hz，1H)，6.88-6.85(m，2H)，6.81-6.79(m，2H)，4.50-4.47(m，1H)，3.74(d，J＝3，0Hz，3H)，3.54-3.51(m，2H)，2.93-2.86(m，1H)，2.68-2.64(m，1H)，2.34-2.32(m，2H)，2.04-1.99(m，1H)，1.90-1.78(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ153.2，144.5，138.1，134.9，129.0，127.0，126.4，126.0，119.6，118.7，114.6，58.9，55.6，43.6，35.3，26.0，22.7，17.0；LRMS(EI，70eV)m/z(％)：306(M + ，4)，223(6)，238(100)，115(13)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 O[M+H] + 307.1805，found 307.1803。
3da: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.19-7.14(m，2H)，7.10(t，J＝10.5Hz，2H)，6.93-6.89(m，2H)，6.83-6.80(m，2H)，4.54-4.50(m，1H)，3.55-3.53(m，2H)，2.94-2.88(m，1H)，2.73-2.67(m，1H)，2.31(t，J＝7.5Hz，2H)，2.05-2.00(m，1H)，1.91-1.80(m，2H)，1.78-1.72(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ156.3(d，J CF ＝236.3Hz)，146.5(d，J CF ＝2.1Hz)，137.7，134.6，128.9，127.0，126.6，126.0，119.5，117.3(d，J CF ＝7.4Hz)，115.6(d，J CF ＝21.8Hz)，58.7，43.0，35.4，26.0，22.7，17.0； 19 F NMR(471MHz，CDCl 3 )δ-125.9；LRMS(EI，70eV)m/z(％)：294(M + ，3)，115(11)，226(100)，95(10)；HRMS m/z(ESI)calcd for C 19 H 19 FN 2 [M+H] + 295.1605，found 295.1600。
3ea: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.29-7.27(m，2H)，7.18-7.15(m，2H)，7.12-7.08(m，2H)，6.73-6.71(m，2H)，4.61-4.58(m，1H)，3.57-3.54(m，2H)，2.98-2.92(m，1H)，2.80-2.74(m，1H)，2.32-2.29(m，2H)，2.09-2.01(m，1H)，1.90-1.78(m，2H)，1.76-1.69(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ148.5，137.4，134.5，131.9，128.7，127.0，126.8，126.1，119.4，116.1，109.6，58.2，42.0，35.3，26.4，22.7，17.0；LRMS(EI，70eV)m/z(％)：354(M + ，17)，253(38)，207(100)，281(32)；HRMS m/z(ESI)calcd for C 19 H 19 BrN 2 [M+H] + 355.0804，found 355.0799。
3fa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.46(d，J＝8.5Hz，2H)，7.21-7.15(m，3H)，7.11(d，J＝5.5Hz，1H)，6.86(d，J＝8.5Hz，2H)，4.75(t，J＝7.5Hz，1H)，3.65(t，J＝7.0Hz，2H)，3.06-3.00(m，1H)，2.92-2.87(m，1H)，2.35(t，J＝7.5Hz，2H)，2.15-2.08(m，1H)，1.96-1.88(m，1H)，1.85-1.72(m，1H)； 13 C NMR(125MHz，Chloroform-d)δ151.4，137.2，134.5，128.7，127.2，127.1，126.7(q，J CF ＝3.8Hz)，126.3，124.8(d，J CF ＝268.2Hz)，119.3，118.7(d，J CF ＝32.5Hz)，112.5，58.2，41.9，35.4，26.9，22.7，17.2； 19 F NMR(471MHz，CDCl 3 )δ-61.1；LRMS(EI，70eV)m/z(％)：344(M + ，4)，172(8)，276(100)，145(11)；HRMS m/z(ESI)calcd for C 20 H 19 F 3 N 2 [M+H] + 345.1573，found 345.1574。
3ga: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.24-7.16(m，4H)，7.09(d，J＝7.5Hz，1H)，7.04-6.96(m，2H)，6.85(d，J＝7.5Hz，1H)，4.33(d，J＝9.0Hz，1H)，3.41-3.35(m，1H)，3.17-3.12(m，1H)，2.75-2.68(m，1H)，2.63-2.59(m，1H)，2.36(s，3H)，2.31-2.23(m，2H)，2.04-1.97(m，1H)，1.89-1.75(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ150.2，138.7，135.5，133.4，131.1，129.1，126.6，126.4，126.2，123.5，122.5，119.7，59.5，44.4，35.3，25.9，22.4，18.1，16.9；LRMS(EI，70eV)m/z(％)：290(M + ，2)，223(17)，222(100)，220(10)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 [M+H] + 291.1856，found 291.1857。
3ha: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.15-7.08(m，5H)，6.68(d，J＝13.0Hz，2H)，6.58(d，J＝7.5Hz，1H)，4.67(t，J＝7.0Hz，1H)，3.66-3.54(m，2H)，3.01-2.94(m，1H)，2.76-2.71(m，1H)，2.31(d，J＝9.0Hz，5H)，2.08-2.02(m，1H)，1.91-1.73(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ149.7，138.9，138.0，134.8，129.1，128.8，127.0，126.6，125.9，119.5，118.9，115.5，111.9，58.1，41.8，35.4，26.4，22.7，21.8，17.0；LRMS(EI，70eV)m/z(％)：290(M + ，12)，207(37)，83(100)，276(35)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 [M+H] + 291.1856，found 291.1858。
3ia: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.71-7.66(m，2H)，7.60(d，J＝8.5Hz，1H)，7.35(t，J＝8.0Hz，1H)，7.24-7.15(m，5H)，7.10(d，J＝7.0Hz，1H)，7.06(s，1H)，4.81(t，J＝7.5Hz，1H)，3.79(t，J＝7.5Hz，1H)，3.66(t，J＝11.0Hz，1H)，3.04-2.97(m，1H)，2.77(d，J＝16.5Hz，1H)，2.31(t，J＝7.5Hz，2H)，2.14-2.07(m，1H)，1.96-1.90(m，1H)，1.87-1.74(m，2H)； 13 C NMR(125MHz，CDCl 3 )δ147.5，137.8，134.8，134.7，129.0，128.9，127.6，127.3，127.1，126.7，126.3，126.3，126.1，122.8，119.5，118.2，109.4，58.2，42.2，35.5，26.5，22.8，17.1；LRMS(EI，70eV)m/z(％)：326(M + ，29)，173(38)，207(100)，168(70)；HRMS m/z(ESI)calcd for C 23 H 22 N 2 [M+H] + 327.1856，found 327.1858。
3ka: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.21(t，J＝8.5Hz，2H)，6.97(t，J＝11.0Hz，2H)，6.92(s，1H)，6.86(d，J＝8.0Hz，2H)，6.74(t，J＝8.0Hz，1H)，4.62(t，J＝7.0Hz，1H)，3.63-3.53(m，2H)，2.95-2.89(m，1H)，2.72-2.67(m，1H)，2.32(d，J＝8.0Hz，5H)，2.06-2.03(m，1H)，1.92-1.81(m，2H)，1.79-1.74(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ149.7，137.7，135.4，131.7，129.2，128.6，127.5，127.4，119.5，117.9，114.8，58.2，42.0，35.5，25.9，22.8，21.0，17.0；LRMS(EI，70eV)m/z(％)：290(M + ，4)，115(6)，222(100)，104(9)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 [M+H] + 291.1856，found 291.1859。
31a: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.24-7.21(m，2H)，7.12(d，J＝6.5Hz，2H)，7.02(d，J＝8.0Hz，1H)，6.87(d，J＝8.0Hz，2H)，6.78(t，J＝8.0Hz，1H)，4.63-4.61(m，1H)，3.71-3.65(m，1H)，3.58-3.51(m，1H)，2.95-2.88(m，1H)，2.69-2.64(m，2H)，2.40-2.34(m，2H)，2.10-2.01(m，1H)，1.93-1.81(m，3H)，1.81-1.74(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ149.5，139.8，133.2，131.4，130.3，129.3，126.8，126.8，119.4，118.6，115.4，58.0，41.6，35.3，25.5，22.8，17.0；LRMS(EI，70eV)m/z(％)：310(M + ，2)，206(9)，242(100)，173(16)；HRMS m/z(ESI)calcd for C 19 H 19 ClN 2 [M+H] + 311.1310，found 311.1310。
3ma: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.25-7.21(m，2H)，7.04-7.01(m，1H)，6.87(d，J＝8.0Hz，2H)，6.77-6.72(m，2H)，6.65(s，1H)，4.62(t，J＝4.5Hz，1H)，3.77(s，3H)，3.63-3.55(m，2H)，2.98-2.92(m，1H)，2.72-2.70(m，1H)，2.34-2.31(m，2H)，2.05-2.02(m，1H)，1.89-1.81(m，2H)，1.79-1.73(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ158.1，149.6，136.2，130.1，129.3，128.0，119.5，118.0，114.8，113.5，112.1，57.7，55.2，41.9，35.6，26.8，22.8，17.1；LRMS(EI，70eV)m/z(％)：306(M + ，13)，207(43)，242(100)，196(16)；HRMS m/z(ESI)calcd for C 20 H 22 N 2 O[M+H] + 307.1805，found 307.1800。
3na: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.23(t，J＝8.0Hz，2H)，7.15(d，J＝8.0Hz，1H)，7.10(s，1H)，7.06(t，J＝7.0Hz，1H)，6.87(d，J＝8.0Hz，2H)，6.79(t，J＝7.5Hz，1H)，4.64(t，J＝4.5Hz，1H)，3.68-3.63(m，1H)，3.59-3.52(m，1H)，2.98-2.92(m，1H)，2.73-2.68(m，1H)，2.37-2.34(m，2H)，2.09-2.03(m，1H)，1.91-1.82(m，2H)，1.81-1.74(m，1H)； 13 C NMR(125MHz，CDCl3)δ149.5，136.8，136.5，132.2，129.4，128.8，128.3，126.2，119.4，118.6，115.3，57.8，41.6，35.4，26.1，22.7，17.1；LRMS(EI，70eV)m/z(％)：310(M + ，3)，244(35)，242(100)，243(19)；HRMS m/z(ESI)calcd for C 19 H 19 ClN 2 [M+H] + 311.1310，found 311.1298。
3oa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.23(t，J＝7.5Hz，2H)，6.89(d，J＝8.0Hz，2H)，6.78(d，J＝7.8Hz，1H)，6.89(d，J＝8.0Hz，2H)，6.77(t，J＝7.5Hz，1H)，6.62-6.58(m，2H)，4.62-4.59(m，1H)，3.88(d，J＝3.0Hz，3H)，3.85(d，J＝3.0Hz，3H)，3.71-3.66(m，1H)，3.59-3.52(m，1H)，2.94-2.88(m，1H)，2.64-2.60(m，1H)，2.40-2.37(m，2H)，2.11-2.04(m，1H)，1.97-1.86(m，2H)，1.84-1.79(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ149.9，147.7，147.2，129.8，129.3，126.8，119.6，118.3，115.3，111.5，109.8，57.9，56.0，55.8，41.9，35.4，25.6，22.8，17.1；LRMS(EI，70eV)m/z(％)：336(M + ，5)，244(34)，242(100)，243(25)；HRMS m/z(ESI)calcd for C 21 H 24 N 2 O 2 [M+H] + 337.1911，found 337.1915。
3ab: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.22(t，J＝8.5Hz，2H)，7.17-7.09(m，3H)，7.06(d，J＝7.5Hz，1H)，6.91(d，J＝8.0Hz，2H)，6.77(t，J＝8.0Hz，1H)，4.75-4.71(m，1H)，3.79-3.76(m，1H)，3.68-3.62(m，1H)，3.00-2.93(m，1H)，2.65-2.61(m，1H)，2.57-2.52(m，1H)，2.39-2.34(m，1H)，2.17-2.10(m，1H)，2.02-1.98(m，1H)，1.80-1.74(m，1H)，1.58-1.51(m，1H)，1.45-1.37(m，2H)，1.29(t，J＝9.0Hz，1H)，0.90(t，J＝7.5Hz，3H)； 13 C NMR(125MHz，CDCl 3 )δ149.9，138.4，134.8，129.3，129.1，127.0，126.5，126.0，119.0，118.6，115.9，57.2，41.5，40.8，36.0，33.2，25.3，22.1，19.6，14.0；LRMS(EI，70eV)m/z(％)：318(M + ，2)，216(2)，208(100)，193(5)；HRMS m/z(ESI)calcd for C 22 H 2 6N 2 [M+H] + 319.2169，found 319.2173。
3ac: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.24-7.13(m，5H)，7.10-7.05(m，1H)，6.90(t，J＝8.5Hz，2H)，6.79(t，J＝7.5Hz，1H)，4.88-4.85(m，0.8H)，4.75-4.72(m，0.2H)，4.23-4.18(m，2H)，3.79-3.75(m，0.8H)，3.62-3.55(m，1.2H)，3.05-2.90(m，2H)，2.75-2.67(m，1H)，2.64-2.57(m，2H)，2.37-2.27(m，1H)，1.38(t，J＝6.5Hz，0.8H)，1.29-1.24(m，3.22H)； 13 C NMR(125MHz，CDCl 3 )δ172.6，172.5，150.0，149.4，137.4，137.0，134.9，134.8，129.3，129.2，127.2，127.1，126.9，126.7，126.2，126.1，119.1，118.9，117.9，117.6，116.5，115.9，61.5，56.4，42.2，41.6，39.4，38.7，37.7，37.5，36.2，25.5，24.9，21.0，20.0，19.7，16.7，14.1，14.0，14.0；LRMS(EI，70eV)m/z(％)：348(M + ，3)，115(13)，238(100)，116(11)；HRMS m/z(ESI)calcd for C 22 H 2 ４N 2 O 2 [M+H] + 349.1911，found 349.1913。
3ad: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.41(t，J＝10.0Hz，1H)，7.34-7.29(m，3H)，7.24(d，J＝7.5Hz，1H)，7.21-7.08(m，5H)，7.01(d，J＝6.5Hz，0.5H)，6.93(d，J＝7.0Hz，0.5H)，6.75-6.63(m，3H)，4.53(t，J＝8.0Hz，0.5H)，4.44(d，J＝11.5Hz，0.5H)，3.89-3.85(m，0.5H)，3.69-3.62(m，0.5H)，3.58-3.52(m，0.5H)，3.48-3.43(m，0.5H)，3.06-2.91(m，1.5H)，2.88-2.84(m，0.5H)，2.64-2.49(m，3.5H)，2.45-2.39(m，0.5H)，2.21-2.12(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ149.7，149.0，141.2，141.2，138.2，137.5，134.9，134.6，129.2，129.2，129.0，129.0，128.7，127.7，127.6，127.5，127.1，127.0，126.8，126.4，125.9，125.8，118.6，118.4，118.3，117.8，115.9，114.3，56.1，55.8，42.5，41.9，40.8，40.6，39.4，38.7，26.6，25.6，24.9，24.7；LRMS(EI，70eV)m/z(％)：352(M + ，23)，238(66)，207(100)，193(33)；HRMS m/z(ESI)calcd for C 25 H 24 N 2 [M+H] + 353.2012，fDund 353.2014。
3ae: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.42-7.37(m，2H)，7.33-7.29(m，3H)，7.13-7.05(m，4H)，6.97(d，J＝7.0Hz，1H)，6.81-6.73(m，2H)，6.62(d，J＝8.0Hz，2H)，4.30(d，J＝10.5Hz，1H)，3.85-3.66(m，2H)，3.22-3.18(m，1H)，2.90-2.79(m，1H)，2.77-2.66(m，2H)，2.48(d，J＝16.5Hz，1H)，2.14(d，J＝15.0Hz，1H)，1.54(s，3H)； 13 C NMR(125MHz，CDCl 3 )δ149.1，144.6，138.4，135.1，130.9，129.2，129.1，128.8，126.9，126.9，126.3，126.0，125.7，119.0，116.9，55.1，48.1，42.3，40.8，29.6，27.8，24.5；LRMS(EI，70eV)m/z(％)：366(M + ，2)，193(7)，208(100)，165(4)；HRMS m/z(ESI)calcd for C 26 H 2 6N 2 [M+H] + 367.2169，found 367.2170。
3af: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.26-7.23(m，2H)，7.18(t，J＝7.0Hz，3H)，7.13(t，J＝4.5Hz，1H)，6.93(t，J＝3.0Hz，2H)，6.79-6.75(m，1H)，4.92-4.89(m，1H)，4.17(t，J＝4.0Hz，2H)，3.95-3.91(m，1H)，3.77-3.73(m，1H)，3.62-3.57(m，2H)，3.03-2.99(m，1H)，2.85-2.80(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ149.2，135.5，134.5，129.3，128.5，127.5，127.2，126.1，118.1，115.8，114.2，74.3，59.0，56.5，42.3，27.3；HRMS m/z(ESI)calcd for C 18 H 1 8N 2 O[M+H] + 279.1492，found 279.1489。
3ag: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.21(t，J＝9.0Hz，5H)，7.14(s，0.5H)7.07(d，J＝7.0Hz，0.5H)，6.90(t，J＝10.5Hz，2H)，6.80-6.75(m，1H)，5.12(t，J＝5.5Hz，0.5H)，4.96(t，J＝8.0Hz，0.5H)，4.68(d，J＝3.0Hz，0.5H)，4.10(d，J＝12.5Hz，0.5H)，4.00-3.85(m，1H)，3.74(d，J＝16.0Hz，1H)，3.66(s，1H)，3.63-3.54(m，2H)，3.09-3.02(m，1H)，2.89-2.79(m，1H)，1.56(d，J＝19.5Hz，9H)； 13 C NMR(125MHz，CDCl 3 )δ154.5，154.1，149.4，149.2，135.6，135.3，135.0，134.9，129.4，128.7，128.7，127.5，127.4，127.2，127.1，126.5，126.3，118.2，118.1，116.0，115.9，114.2，113.9，82.2，82.0，80.9，58.8，58.3，51.8，51.0，42.2，41.4，37.3，36.3，28.3，28.2，26.9，26.5；LRMS(EI，70eV)m/z(％)：377(M + ，5)，244(30)，242(100)，243(17)；HRMS m/z(ESI)calcd for C 23 H 2 7N 3 O 2 [M+H] + 378.2176，found 378.2175。
3ah: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.21-7.11(m，6H)，6.92(d，J＝8.0Hz，2H)，6.72(t，J＝7.5Hz，1H)，4.63(s，1H)，3.89-3.83(m，1H)，3.62-3.56(m，1H)，2.96(t，J＝7.0Hz，2H)，2.19(t，J＝6.5Hz，2H)，1.63(d，J＝10.5Hz，2H)，1.51(t，J＝6.5Hz，2H)，1.01(s，3H)，0.93(s，3H)； 13 C NMR(125MHz，CDCl 3 )δ151.6，136.2，135.6，129.1，128.7，128.6，126.7，125.2，119.7，117.9，115.9，65.0，44.8，41.3，39.9，26.8，25.5，20.8，17.8；LRMS(EI，70eV)m/z(％)：318(M + ，9)，317(20)，207(100)，267(30)；HRMS m/z(ESI)calcd for C 22 H 26 N 2 [M+H] + 319.2169，found 319.2168。
3ai: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.28(t，J＝8.5Hz，1H)，7.22-7.15(m，3.5H)，7.13-7.07(m，3.5H)，6.99(d，J＝7.5Hz，1H)，6.93-6.89(m，1.5H)，6.82(d，J＝7.5Hz，1H)，6.74(d，J＝8.0Hz，1.5H)，6.64(t，J＝8.0Hz，0.5H)，6.50(d，J＝8.0Hz，0.5H)，4.87(d，J＝7.0Hz，0.5H)，4.82(d，J＝7.0Hz，0.5H)，3.62-3.56(m，0.5H)，3.52-3.47(m，0.5H)，3.41-3.31(m，1H)，3.19-3.12(m，1H)，2.97-2.91(m，0.5H)，2.85-2.79(m，0.5H)，2.73-2.67(m，0.5H)，2.22-2.11(m，2H)，2.10-2.00(m，1H)，1.86-1.75(m，1.5H)，1.58-1.47(m，2H)，1.21-1.15(m，2H)； 13 C NMR(125MHz，CDCl 3 )δ149.9，149.4，141.5，141.3，136.8，135.9，135.7135.3，129.3，129.2，129.2，128.9，128.6，128.6，128.5，128.1，128.0，127.8，126.8，126.7，126.7，126.5，125.2，125.0，119.6，118.8，117.2，116.7，114.3，112.7，64.4，64.0，51.7，51.3，43.0，42.7，31.6，31.4，27.0，26.9，26.7，25.4，17.0，16.9；HRMS m/z(ESI)calcd for C 27 H 28 N 2 [M+H] + 381.2325，found 381.2325。
the synthesis strategy is applied to the structural modification of the alpha-aminocarbonyl compounds. That is, under the reaction conditions of example 1, various α -aminocarbonyl compounds were obtained in place of the N-phenyltetrahydroisoquinoline represented by formula 1a, and the reaction was carried out with the cyclobutanone oxime ester compound represented by formula 2a, with the following results:
structural characterization of the product:
5aa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.18(t，J＝8.5Hz，2H)，6.76(t，J＝7.0Hz，1H)，6.62(d，J＝8.0Hz，2H)，4.21-4.17(m，3H)，4.08(t，J＝6.5Hz，1H)，2.40-2.36(m，2H)，2.04-1.98(m，1H)，1.93-1.86(m，1H)，1.84-1.78(m，2H)，1.25(t，J＝7.5Hz，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.3，146.4，129.3，119.1，118.6，113.5，61.4，55.9，31.6，21.7，16.9，14.1；LRMS(EI，70eV)m/z(％)：246(M + ，9)，132(25)，173(100)，120(30)；HRMS m/z(ESI)calcd for C 14 H 18 N 2 O 2 [M+H] + 247.1441，found 247.1438。
5ba: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.17(t，J＝8.0Hz，2H)，6.75(t，J＝7.5Hz，1H)，6.62(d，J＝8.0Hz，2H)，4.17(s，1H)，3.99(t，J＝5.0Hz，1H)，2.42-2.37(m，2H)，2.01-1.95(m，1H)，1.91-1.88(m，1H)，1.84-1.78(m，2H)，1.44(s，9H)； 13 C NMR(125MHz，CDCl 3 )δ172.4，146.6，129.3，119.2，118.4，113.5，82.2，56.4，31.6，27.9，21.6，17.0；LRMS(EI，70eV)m/z(％)：274(M + ，4)，118(23)，173(100)，104(10)；HRMS m/z(ESI)calcd for C 16 H 22 N 2 O 2 [M+H] + 275.1754，found 275.1759。
5ca: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.34(t，J＝7.5Hz，3H)，7.28(d，J＝7.0Hz，2H)，7.17(t，J＝7.5Hz，2H)，6.76(t，J＝7.0Hz，1H)，6.61(d，J＝8.0Hz，2H)，5.18-5.12(m，2H)，4.30-4.09(m，2H)，2.36-2.28(m，2H)，2.04-1.97(m，1H)，1.93-1.85(m，1H)，1.77-1.71(m，2H)； 13 C NMR(125MHz，CDCl 3 )δ173.2，146.4，135.2，129.4，128.6，128.5，128.3，119.0，118.8，113.6，67.1，56.0，31.6，21.6，16.9；LRMS(EI，70eV)m/z(％)：308(M + ，5)，120(23)，173(100)，91(59)；HRMS m/z(ESI)calcd for C 19 H 20 N 2 O 2 [M+H] + 309.1598，found 309.1593。
5da: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ6.98(d，J＝7.5Hz，2H)，6.54(d，J＝7.5Hz，2H)，4.20-4.15(m，2H)，4.04(d，J＝9.0Hz，2H)，2.40-2.33(m，2H)，2.22(s，3H)，2.02-1.95(m，1H)，1.90-1.84(m，1H)，1.83-1.76(m，2H)，1.24(t，J＝7.5Hz，3H)； 13 C NMR(125MHz，CDCl3)δ173.4，144.1，129.7，127.8，119.1，113.7，61.2，56.2，31.6，21.7，20.2，16.8，14.1；LRMS(EI，70eV)m/z(％)：260(M + ，13)，134(18)，187(100)，146(14)；HRMS m/z(ESI)calcd for C 15 H 20 N 2 O 2 [M+H] + 261.1598，found 261.1601。
5ea: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ6.78-6.75(m，2H)，6.61-6.59(m，2H)，4.19-4.15(m，2H)，3.99-3.93(m，2H)，3.73(d，J＝2.0Hz，3H)，2.40-2.36(m，2H)，1.99-1.94(m，1H)，1.88-1.79(m，3H)，1.25-1.22(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.5，152.8，140.5，119.1，115.2，114.7，61.1，57.0，55.5，31.7，21.7，16.8，14.1；LRMS(EI，70eV)m/z(％)：276(M + ，18)，162(12)，203(100)，134(22)；HRMS m/z(ESI)calcd for C 15 H 20 N 2 O 3 [M+H] + 277.1547，found 277.1544。
5fa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.14-7.11(m，2H)，6.55(d，J＝9.0Hz，2H)，4.21-4.18(m，3H)，4.05-4.01(m，1H)，2.45-2.35(m，2H)，2.04-1.97(m，1H)，1.93-1.86(m，1H)，1.83-1.77(m，2H)，1.28-1.25(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.0，145.1，129.2，123.3，119.0，114.7，61.5，56.0，31.5，21.6，16.9，14.1；LRMS(EI，70eV)m/z(％)：280(M + ，10)，203(24)，207(100)，209(32)；HRMS m/z(ESI)calcd for C 14 H 17 ClN 2 O 2 [M+H] + 281.1051，found 281.1048。
5ga: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.11-7.07(m，2H)，6.72-6.69(m，1H)，6.54(t，J＝3.0Hz，1H)，4.23-4.18(m，2H)，4.14(t，J＝7.5Hz，1H)，2.42-2.37(m，2H)，2.21(d，J＝3.0Hz，3H)，2.07-2.01(m，1H)，1.99-1.93(m，1H)，1.86-1.79(m，2H)，1.29-1.25(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.4，144.5，130.4，127.0，123.0，119.1，118.2，110.4，61.4，55.8，31.7，21.7，17.4，16.9，14.1；LRMS(EI，70eV)m/z(％)：260(M + ，10)，188(14)，187(100)，146(16)；HRMS m/z(ESI)calcd for C 15 H 2 0N2O 2 [M+H] + 261.1598，found 261.1593。
5ha: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.45(d，J＝8.0Hz，1H)，7.16(t，J＝8.0Hz，1H)，6.63(t，J＝8.0Hz，1H)，6.58(d，J＝8.0Hz，1H)，4.83(d，J＝8.5Hz，1H)，4.25-4.20(m，2H)，4.14(d，J＝7.0Hz，1H)，2.44-2.40(m，2H)，2.11-2.05(m，1H)，2.03-1.95(m，1H)，1.86-1.80(m，2H)，1.28(d，J＝8.5Hz，3H)； 13 C NMR(125MHz，CDCl 3 )δ172.5，143.4，132.8，128.5，119.1，119.0，111.8，110.6，61.7，55.9，31.4，21.6，17.0，14.2；LRMS(EI，70eV)m/z(％)：324(M + ，10)，210(15)，251(100)，184(22)；HRMS m/z(ESI)calcd for C 14 H 17 BrN 2 O 2 [M+H] + 325.0546，found 325.0544。
5ia: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.06(t，J＝8.0Hz，1H)，6.58(d，J＝7.5Hz，1H)，6.44(t，J＝7.5Hz，2H)，4.22-4.18(m，2H)，4.13-4.07(m，2H)，2.41-2.37(m，2H)，2.27(s，3H)，2.02-1.98(m，1H)，1.91-1.87(m，1H)，1.84-1.80(m，2H)，1.26(t，J＝7.0Hz，3H)； 13 C NMR(125MHz，CDCl3)δ173.3，146.5，139.2，129.2，119.6，119.1，114.4，110.6，61.4，55.9，31.7，21.7，21.5，16.9，14.2；LRMS(EI，70eV)m/z(％)：260(M + ，10)，146(16)，187(100)，118(23)；HRMS m/z(ESI)calcd for C 15 H 2 0N2O 2 [M+H] + 261.1598，found 261.1599。
5ja: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ6.42(s，1H)，6.26(s，2H)，4.22-4.17(m，2H)，4.11-4.06(m，2H)，2.40-2.36(m，2H)，2.22(d，J＝2.5Hz，6H)，2.02-1.96(m，1H)，1.91-1.85(m，1H)，1.83-1.77(m，2H)，1.28-1.25(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.4，146.5，139.0，120.6，119.1，111.4，61.3，55.8，31.7，21.7，21.4，16.9，14.1；LRMS(EI，70eV)m/z(％)：274(M + ，16)，160(14)，201(100)，148(13)；HRMS m/z(ESI)calcd for C 16 H 2 2N 2 O 2 [M+H] + 275.1754，found 275.1759。
5ka: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.67-7.59(m，3H)，7.36(t，J＝7.5Hz，1H)，7.22(t，J＝7.5Hz，1H)，6.90(d，J＝9.0Hz，1H)，6.79(s，1H)，4.38(d，J＝7.5Hz，1H)，4.23-4.18(m，3H)，2.39-2.31(m，2H)，2.08-2.02(m，1H)，1.97-1.90(m，1H)，1.84-1.78(m，2H)，1.25(t，J＝7.5Hz，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.2，144.1，134.8，129.2，127.9，127.5，126.4，126.0，122.5，119.1，118.1，105.5，61.4，55.8，31.4，21.6，16.9，14.1；LRMS(EI，70eV)m/z(％)：296(M + ，14)，168(25)，223(100)，173(40)；HRMS m/z(ESI)calcd for C 18 H 2 0N2O 2 [M+H] + 297.1598，found 297.1593。
51a: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.92-7.90(m，1H)，7.79(t，J＝6.0Hz，1H)，7.49-7.46(m，2H)，7.33-7.28(m，2H)，6.56(d，J＝6.5Hz，1H)，4.94(d，J＝8.0Hz，1H)，4.31-4.22(m，3H)，2.46-2.37(m，2H)，2.18-2.12(m，1H)，2.10-2.03(m，1H)，1.91-1.84(m，2H)，1.30-1.27(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.4，141.6，134.4，128.6，126.2，126.，125.1，123.9，120.0，119.1，118.8，105.3，61.6，55.9，31.4，21.8，17.0，14.2；LRMS(EI，70eV)m/z(％)：296(M + ，20)，224(19)，223(100)，182(17)；HRMS m/z(ESI)calcd for C 18 H 20 N 2 O 2 [M+H] + 297.1598，found 297.1599。
5ma: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.17(t，J＝8.0Hz，2H)，6.73(t，J＝8.0Hz，1H)，6.62(d，J＝8.0Hz，2H)，4.56(d，J＝8.0Hz，1H)，4.22(d，J＝7.5Hz，1H)，3.61-3.56(m，1H)，3.54-3.49(m，2H)，3.46(t，J＝7.5Hz，1H)，2.42-2.36(m，2H)，2.03-1.97(m，3H)，1.89-1.80(m，5H)； 13 C NMR(125MHz，CDCl 3 )δ170.7，146.9129.4，119.4，118.2，113.6，54.5，46.4，46.1，30.9，26.1，24.0，21.2，17.0；LRMS(EI，70eV)m/z(％)：271(M + ，5)，120(24)，173(100)，132(19)；HRMS m/z(ESI)calcd for C 16 H 21 N 3 O[M+H] + 272.1757，found 272.1758。
5na: yellow oily liquid; yellow oil; 1 H NMR(500MHz，CDCl 3 )：δ7.98(d，J＝8.0Hz，2H)，7.62(t，J＝7.5Hz，1H)，7.51(t，J＝7.5Hz，2H)，7.18(t，J＝7.5Hz，2H)，6.74(t，J＝7.0Hz，1H)，6.69(d，J＝8.0Hz，2H)，5.11(t，J＝5.0Hz，1H)，4.70(s，1H)，2.31(t，J＝6.5Hz，2H)，2.17-2.12(m，1H)，1.84-1.77(m，2H)，1.75-1.69(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ199.7，146.6，134.6，134.0，129.4，129.0，128.3，119.1，118.4，113.6，57.1，31.8，21.1，17.0；HRMS m/z(ESI)calcd for C 18 H 18 N 2 O[M+H] + 279.1492，found279.1496。
5oa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.33(d，J＝4.0Hz，4H)，7.24(d，J＝4.5Hz，1H)，7.09(t，J＝7.5Hz，2H)，6.66(t，J＝7.5Hz，1H)，6.53(d，J＝8.0Hz，2H)，4.36(t，J＝6.9Hz，1H)，4.04(s，1H)，2.37-2.33(m，2H)，2.02-1.91(m，2H)，1.84-1.78(m，1H)，1.72-1.66(m，1H)； 13 C NMR(125MHz，CDCl 3 )δ146.9，142.9，129.2，128.8，127.4，126.3，119.3，117.7，113.4，57.4，37.3，22.4，17.1；HRMS m/z(ESI)calcd for C 17 H 18 N 2 [M+H] + 251.1543，found 251.1538。
the synthesis strategy is applied to structural modification of short peptide compounds. Namely, under the reaction conditions of example 1, the following results were obtained by reacting various short peptide compounds instead of N-phenyltetrahydroisoquinoline represented by formula 1a with a cyclobutanonoxime ester compound represented by formula 2 a:
structural characterization of the product:
5qa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.17(t，J＝8.5Hz，2H)，6.73(d，J＝8.0Hz，1H)，6.62-6.55(m，2H)，4.54-4.50(m，2H)，4.28(s，1H)，3.73(s，3H)，3.69(t，J＝5.0Hz，2H)，2.43-2.34(m，2H)，2.26-2.19(m，1H)，2.12-2.02(m，2H)，2.02-1.97(m，2H)，1.89-1.78(m，4H)； 13 C NMR(125MHz，CDCl 3 )δ172.2，171.1，146.7，129.4，119.4，118.3，113.7，113.6，58.9，54.3，52.2，46.9，30.7，28.7，24.9，20.8，17.0；LRMS(EI，70eV)m/z(％)：329(M + ，1)，244(31)，242(100)，173(20)；HRMS m/z(ESI)calcd for C 18 H 23 N 3 O 3 [M+H] + 330.1812，found 330.1809。
1 H NMR(500MHz，CDCl 3 )δ7.18(t，J＝8.0Hz，2H)，6.78-6.72(m，1H)，6.62(d，J＝8.0Hz，2H)，4.50-4.43(m，2H)，4.26(d，J＝7.5Hz，1H)，3.84-3.78(m，1H)，3.65(d，J＝3.0Hz，3H)，3.62-3.54(m，1H)，2.43-2.34(m，2H)，2.25-2.18(m，1H)，2.13-2.07(m，1H)，2.03(t，J＝8.5Hz，3H)，1.86-1.77(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ172.2，171.0，146.5，129.3，119.3，118.2，113.4，59.2，54.5，52.1，46.8，30.4，28.8，24.7，21.1，16.9。
5qh: yellow oily liquid; 1H NMR (500 MHz, CDCl 3) delta 7.18 (d, J=8.0 Hz, 2H), 6.78-6.74 (m, 1H), 6.66 (d, J=8.0 Hz, 2H), 4.54-4.44 (m, 2H), 4.40-4.28 (m, 2H), 3.93-3.89 (m, 1H), 3.85-3.80 (m, 2H), 3.74 (t, J=2.0 Hz, 3H), 3.70-3.59 (m, 2H), 2.24-2.18 (m, 1H), 2.12-2.07 (m, 1H), 2.03-1.96 (m, 2H); 13C NMR (125 mhz, cdcl 3) delta 172.3, 172.1, 169.7, 169.6, 146.2, 146.0, 129.4, 129.4, 118.7, 118.5, 115.8, 115.6, 113.7, 113.4, 72.0, 71.5, 59.2, 59.0, 56.9, 56.8, 55.2, 55.0, 52.3, 52.2, 47.1, 47.0, 29.0, 28.9, 24.8, 24.7; HRMS M/z (ESI) calcd for C17H21N3O4[ M+H ] +332.1605,found 332.1601.
5ra: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.21-7.15(m，2H)，6.80(t，J＝8.0Hz，1H)，6.63(d，J＝7.5Hz，2H)，4.42-4.36(m，1H)，4.14-4.04(m，1H)，3.81-3.75(m，1H)，2.44-2.37(m，2H)，2.13-2.07(m，2H)，2.04-1.91(m，2H)，1.89-1.82(m，2H)，1.45(s，5H)，1.32(s，4H)，1.26(t，J＝7.5Hz，1H)，0.90-0.86(m，3H)，0.80(d，J＝6.5Hz，1H)，0.69(d，J＝7.0Hz，1H)； 13 C NMR(125MHz，CDCl 3 )δ172.4，172.2，170.8，170.0，146.3，146.1，129.3，119.3，119.2，119.2，113.8，113.5，82.0，81.9，58.9，58.5，57.6，57.0，32.5，32.3，31.4，31.1，27.9，27.7，22.2，22.1，18.9，18.8，17.7，17.1，16.9，16.9；LRMS(EI，70eV)m/z(％)：373(M + ，2)，242(13)，173(100)，222(10)；HRMS m/z(ESI)calcd for C 21 H 31 N 3 O 3 [M+H] + 374.2438，found 374.2435。
5sa: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.20(t，J＝7.5Hz，2H)，6.81(t，J＝7.5Hz，1H)，6.66-6.61(m，2H)，4.62-4.53(m，1H)，4.11-4.05(m，1H)，3.77-3.72(m，3H)，3.67(d，J＝2.5Hz，1H)，2.45-2.36(m，2H)，2.11-2.07(m，1H)，1.97-1.90(m，2H)，1.88-1.83(m，2H)，1.39(d，J＝7.5Hz，1H)，1.33(d，J＝7.0Hz，2H)； 13 C NMR(125MHz，CDCl 3 )δ173.0，172.7，172.5，172.3，146.3，146.3，129.4，129.3，119.3，119.3，119.2，119.1，113.8，113.5，60.3，58.6，52.4，52.3，47.9，47.7，32.3，22.1，21.9，18.0，17.9，16.9，16.9；HRMS m/z(ESI)calcd for C 16 H 21 N 3 O 3 [M+H] + 304.1656，found 304.1652。
5ta: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.23-7.18(m，2H)，7.04-6.97(m，1H)，6.85-6.81(m，1H)，6.66-6.61(m，2H)，4.61-4.57(m，1H)，3.95(d，J＝20.5Hz，1H)，3.78-3.72(m，3H)，3.64(d，J＝3.0Hz，1H)，2.46-2.38(m，2H)，2.12-2.06(m，1H)，1.98-1.92(m，1H)，1.90-1.82(m，2H)，1.60-1.50(m，2H)，1.46-1.34(m，1H)，0.93-0.90(m，3H)，0.85-0.78(m，3H)； 13 C NMR(125MHz，CDCl 3 )δ173.2，172.6，172.4，171.2，146.3，146.1，129.4，129.4，119.6，119.5，119.2，119.2，114.0，113.6，58.9，58.5，52.3，52.2，50.6，50.3，41.0，32.4，32.4，24.9，24.6，22.8，22.7，22.2，22.0，21.7，21.4，17.0；LRMS(EI，70eV)m/z(％)：345(M + ，3)，207(7)，173(100)，120(24)；HRMS m/z(ESI)calcd for C 19 H 2 7N 3 O 3 [M+H] + 346.2125，found 346.2130。
5ua: yellow oily liquid; 1 H NMR(500MHz，CDCl 3 )δ7.23-7.18(m，2H)，6.84-6.79(m，1H)，6.665-6.60(m，2H)，4.64-4.52(m，1H)，4.06-4.02(m，1H)，3.79-3.74(m，1H)，2.45-2.38(m，3H)，2.28-2.24(m，1H)，2.14-2.08(m，2H)，2.06(d，J＝3.5Hz，2H)，1.96-1.92(m，3H)，1.89-1.83(m，3H)，1.45(d，J＝3.0Hz，5H)，1.36(d，J＝3.0Hz，4H)； 13 C NMR(125MHz，CDCl3)δ172.4，172.2，170.6，160.0，146.3，146.1，129.4，129.4，119.3，119.2，113.7，113.4，82.4，82.3，58.6，58.4，52.2，51.6，32.3，31.8，31.4，29.9，29.6，27.9，27.7，22.2，22.1，17.0，16.9，15.4，15.2，14.1；LRMS(EI，70eV)m/z(％)：405(M + ，22)，281(43)，207(100)，177(44)；HRMS m/z(ESI)calcd for C 21 H 31 N 3 O 3 S[M+H] + 406.2159，found406.2157。
the above-described embodiments are merely preferred embodiments of the present application and are not intended to be exhaustive of the possible implementations of the present application. Any obvious modifications thereof, without departing from the principles and spirit of the present application, should be considered to be within the scope of the appended claims.

Claims (16)

1. Photo-redox catalytic N-aryl amine and cyclic ketoxime ester C (sp) 3 )-C(sp 3 ) A cross-coupling method comprising the steps of:
sequentially adding an N-arylamine compound shown in a formula 1, a cyclic ketoxime ester compound shown in a formula 2, a photocatalyst and an organic solvent into a reactor, then placing the reactor under room temperature and illumination for stirring reaction under the condition of protective atmosphere, and obtaining a target product shown in a formula 3 after the reaction is completed; the reaction formula is as follows:
in the above-mentioned reaction scheme, the reaction mixture,represents a substituted or unsubstituted phenyl or naphthyl group; wherein the substituents are selected from F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, trifluoromethyl;
R 1 selected from hydrogen, methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl;
R 2 selected from methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl, -C (O) OR 6 、-C(O)R 7 、-C(O)NR 8 R 9 ；
Wherein R is 6 、R 7 Selected from methyl, ethyl, t-butyl, phenyl, naphthyl, benzyl;
R 8 ,R 9 independently of one another, selected from methyl, ethyl, tert-butyl, phenyl, naphthyl, benzyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl OR isopentyl substituted with R ', where R' is selected from methoxy, ethoxy, tert-butoxy, methylthio, ethylthio, -C (O) OR 6 、-C(O)R 7 And/or R 8 ,R 9 Are connected to each other and to the connection R 8 ,R 9 Together form a substituted or unsubstituted tetrahydropyrrole structure, wherein the substituentsis-C (O) OR 6 、-C(O)R 7 ；
And/or R 1 ,R 2 The N-arylamine compounds represented by formula 1 at this time have the structure represented by the following formula 1', being linked to each other:the target product represented by formula 3 has a structure represented by the following formula 3': />Wherein R' is selected from F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, trifluoromethyl;
R 3 selected from hydrogen, F, cl, br, I, methyl, ethyl, t-butyl, methoxy, ethoxy, t-butoxy, phenyl, naphthyl, benzyl;
x is selected from O, S, N or C, R when X is O, S 4 ,R 5 Absence of; when X is N, R 4 ,R 5 One is absent; when X is C, R 4 ,R 5 Presence;
R 4 ,R 5 independently of one another, from the group consisting of hydrogen, methyl, ethyl, n-propyl, phenyl, naphthyl, benzyl, -C (O) OR 6 、-C(O)R 7 ；
n is an integer selected from 1, 2, 3 or 4;
ar is selected from substituted or unsubstituted phenyl or naphthyl, wherein the substituents are halogen, F, cl, br, I, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl;
wherein the photocatalyst is 3CzClIPN, fac-Ir (ppy) 3 ，Ru(bpy) 3 Cl 2 ，Eosin Y，[Acr][MesClO 4 ]Rhodamine B, methylene blue or a mixture of any one or more of the rhodamine B, the methylene blue and the mixture of the rhodamine B.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,represents a substituted or unsubstituted phenyl group, an unsubstituted naphthyl group; wherein the substituents are selected from F, cl, br, methyl, methoxy, trifluoromethyl;
R 1 selected from hydrogen;
R 2 selected from phenyl, -C (O) OR 6 、-C(O)R 7 、-C(O)NR 8 R 9 ；
Wherein R is 6 、R 7 Selected from methyl, ethyl, t-butyl, phenyl;
R 8 ,R 9 independently of one another, selected from methyl, ethyl, n-propyl, isobutyl OR isopentyl substituted by R ', where R' is selected from methylthio, -C (O) OR 6 And/or R 8 ,R 9 Are connected to each other and to the connection R 8 ,R 9 Together form a substituted OR unsubstituted tetrahydropyrrole structure, wherein the substituents are-C (O) OR 6 ；
And/or R 1 ,R 2 The N-arylamine compounds represented by formula 1 at this time have the structure represented by the following formula 1', being linked to each other:the target product represented by formula 3 has a structure represented by the following formula 3': />Wherein R' is selected from F, cl, br, methyl, methoxy, trifluoromethyl;
R 3 selected from hydrogen, methyl, phenyl;
x is selected from O, N or C, when X is O, R 4 ,R 5 Absence of; when X is N, R 4 ,R 5 One is absent; when X is C, R 4 ,R 5 Presence;
R 4 ,R 5 independently of one another, from the group consisting of hydrogen, methyl, ethyl, n-propyl, phenyl, -C (O) OR 6 ；
n is an integer selected from 1, 2 and 3;
ar is selected from trifluoromethyl substituted phenyl.
3. The method according to any one of claims 1 to 2, wherein the photocatalyst is 3CzClIPN.
4. The method according to any one of claims 1 to 2, wherein the organic solvent is selected from any one or a mixture of several of acetonitrile, dichloroethane, methanol, DMSO.
5. The method of claim 4, wherein the organic solvent is selected from acetonitrile.
6. The method according to any one of claims 1-2, wherein the protective atmosphere is an argon atmosphere or a nitrogen atmosphere.
7. The method of claim 6, wherein the protective atmosphere is an argon atmosphere.
8. A method according to any one of claims 1-2, wherein the illumination is provided by a 5W LED blue light lamp.
9. The method according to any one of claims 1 to 2, wherein the molar ratio of the N-arylamine compound represented by formula 1, the cyclic ketoxime ester compound represented by formula 2, and the photocatalyst is 1 (1 to 3) (0.01 to 0.1).
10. The method according to claim 9, wherein the molar ratio of the N-arylamine compound represented by formula 1, the cyclic ketoxime ester compound represented by formula 2, and the photocatalyst is 1:1.2-1.5:0.03-0.05.
11. The method according to claim 10, wherein the molar ratio of the N-arylamine compound represented by formula 1, the cyclic ketoxime ester compound represented by formula 2, and the photocatalyst is 1:1.2:0.03.
12. The method according to any one of claims 1 to 2, wherein the reaction time of the stirred reaction is 4 to 48 hours.
13. The method according to claim 12, wherein the reaction time of the stirring reaction is 8 to 36 hours.
14. The method according to claim 13, wherein the reaction time of the stirring reaction is 12 to 24 hours.
15. The method of claim 14, wherein the reaction time of the stirred reaction is 12 hours.
16. A method according to any one of claims 1-2, characterized in that the post-treatment operation is as follows: the reaction solution was filtered, concentrated under reduced pressure, and the residue was separated by silica gel column chromatography to obtain the objective product represented by formula 3.
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