CN115850150A - Method for synthesizing 3-tetra-substituted indoline-2-ketone compound by one-pot method - Google Patents
Method for synthesizing 3-tetra-substituted indoline-2-ketone compound by one-pot method Download PDFInfo
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Abstract
The invention belongs to the field of organic chemical medicines, and relates to a method for synthesizing 3-tetra-substituted indoline-2-ketone compounds by a one-pot method. According to the method, aniline derivatives, 3-diazoindolinone derivatives and allyl carbonate derivatives are used as raw materials, rhodium salt, palladium salt and phosphine ligand are used as catalysts, a proper amount of solvent is added, sealed argon gas is filled for reaction, the reaction is stirred at the temperature close to room temperature for a period of time, the solvent is evaporated under reduced pressure after the reaction is finished, and the target product is obtained by silica gel column chromatography or recrystallization separation of the product; realizes the synthesis of the 3-tetra-substituted indoline-2-ketone compound by a three-component one-pot method. The method has the advantages that: the method has the advantages of easily available raw materials, wide substrate adaptability, mild reaction conditions, simpler operation, high efficiency and better atom economy, and better meets the requirement of green chemistry.
Description
Technical Field
The invention belongs to the field of organic chemical medicines, and relates to a method for synthesizing a 3-tetra-substituted indoline-2-one compound by three components of a metal rhodium salt, a metal palladium salt and a phosphine ligand catalyzed aniline derivative, a 3-diazoindoline-2-one derivative and allyl carbonate through a series reaction.
Background
Indolinone compounds are common structures in natural products, drug molecules, and pesticide molecules. They have a wide range of biological activities, such as antibacterial, anticonvulsant, antitumor, antidepressant and anti-aids virus (Hu, w., et al. Org.lett.2019,21,9878, banerjee, a., et al.acc.chem.res.2007,40,151.
Their synthesis attracts more and more attention in view of their particular structure and application. The conventional synthesis of indolinones is mainly the synthesis of indolinones by oxidation of indoles (Schmid, w., et al. This method also has limitations due to limitations in its substrate applicability. Another approach is the synthesis of indolinone compounds (Lin, w., et al. Tetrahedron lett.2014,55,2238) by reduction of indoloquinones. The 3-indolin-2-one is introduced three-dimensionally into the quaternary carbon center of the spiro structure (Hu, w., et al. Adv. Synth. Cat., 2017, 359,58).
The invention fully utilizes the carbene precursor 3-diazoindoline-2-ketone derivative to form Rh carbene under the catalysis of Rh salt, carries out C-H bond insertion on para position of a aniline derivative, and then carries out catalytic allylation with third component raw material allyl carbonate through pd and ligand cooperative relay. Thus, three components of aniline derivatives, 3-diazoindoline-2-ketone derivatives and allyl carbonate are subjected to one-pot series reaction through bimetallic relay catalysis, two active groups, namely p-aminophenyl and allyl, are simultaneously introduced into the 4-position of indoline-2-ketone, and a new quaternary carbon center is constructed. The method has the advantages of easily available raw materials, simple operation, high atom economy and environmental friendliness, and greatly enriches the synthesis methods and types of indolinone derivatives.
Disclosure of Invention
The invention belongs to the field of organic chemical medicines, and relates to a method for synthesizing a 3-tetra-substituted indoline-2-ketone compound by three components of a metal rhodium salt, a metal palladium salt and a phosphine ligand catalyzed aniline derivative, a 3-diazoindoline-2-ketone derivative and allyl carbonate through a series reaction.
The invention synthesizes 3-tetra-substituted indoline-2-ketone compounds by a one-pot method, firstly, rhodium catalyst, palladium catalyst and phosphine ligand are added in the reaction, then a proper amount of solvent is added, aniline derivatives, 3-diazoindoline-2-ketone derivatives and allyl carbonate derivatives are added under the protection of argon gas, the mixture is stirred and reacted for a certain time near the room temperature, the solvent is evaporated under reduced pressure after the reaction is finished, silica gel is used for adsorption, and the target product is obtained by column chromatography or mixed solvent recrystallization separation; purifying by a column chromatography separation method after the reaction, and purifying the product by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent or an ethyl acetate/petroleum ether system as a recrystallization solvent to obtain a pure 3-tetra-substituted indoline-2-ketone compound.
The synthesis method of the 3-tetra-substituted indoline-2-ketone compound comprises the following steps:
R 1 is benzyl, methyl, phenyl, p-toluenesulfonyl; r 2 Is hydrogen, 4-bromine, 5-methyl, 6-fluorine, 6-methoxy, 7-methyl; (R) 3 ) 2 Is dibenzyl, 1,4-butylidene or bis (2-methoxyethyl); r is 4 Is hydrogen, 3-methyl, 3-methoxy, 3-methoxycarbonyl, 2-methyl; r 5 Is hydrogen, phenyl, 4-methoxyphenyl, 4-chlorophenyl, 3-methylphenyl, 3-chlorophenyl, 2-methylphenyl, piperonyl-4-yl.
The aniline derivative has the following structure:
the 3-diazoindolin-2-one has the following structure:
the allyl carbonate derivative has the following structure:
the rhodium catalyst used is Rh 2 (OAc) 4 、Rh 2 (PTTL) 4 、Rh 2 (Oct) 4 、Rh 2 (esp) 2 、Rh 2 (OPiv) 4 (ii) a The palladium catalyst is Pd (OAc) 2 、Pd(PhCN) 2 Cl 2 、Pd(TFA) 2 、Pd 2 (dba) 3 、Pd[(allyl)Cl] 2 (ii) a The phosphine ligand is Xantphos, XPhos, davePhos, BINAP, SPhos,
Equivalence ratio [ Rh]：[Pd]: [ ligand ]]: 1-2% of aniline derivative: 1-5%: 3 to 12 percent.
Aniline derivatives: 3-diazoindolin-2-one: the equivalent ratio of the allyl carbonate derivative is: 1:1 to 2:1 to 2.
Adding a rhodium catalyst, a palladium catalyst and a phosphine ligand, adding a proper amount of solvent, protecting with argon, adding an aniline derivative, a 3-diazoindolinone derivative and an allyl carbonate derivative under the condition of introducing argon, stirring and reacting at the room temperature for 3-36 hours, evaporating the solvent under reduced pressure after the reaction is finished, and performing silica gel column chromatography on the product [ eluent: purifying V (ethyl acetate)/V (petroleum ether) =1/10] to obtain a product, or performing recrystallization purification by using an ethyl acetate/petroleum ether system.
The reaction solvent is an organic solvent. The organic solvent is one of toluene, xylene, acetonitrile, tetrahydrofuran, chloroform and dichloromethane.
Preferably: the rhodium catalyst being Rh 2 (PTTL) 4 (ii) a The palladium catalyst is Pd 2 (dba) 3 (ii) a The ligand is XPhos; the solvent is DCM; rh 2 (PTTL) 4 ：Pd 2 (dba) 3 And XPhos ligand are preferably in a molar ratio of 1.
The concentration of the aniline derivative in the solvent is 0.05-0.2 mol/L.
The invention synthesizes the 3-tetra-substituted indoline-2-ketone compound.
The invention realizes that the aniline derivative, the 3-diazoindoline-2-ketone derivative and the allyl carbonate derivative are used as raw materials and are subjected to bimetallic relay catalysis and condition screeningIn the simple one-pot feeding method, substituted p-aminophenyl and substituted allyl are introduced into three positions of the indoline-2-one derivative at the same time, and a new quaternary carbon center is constructed, so that the novel indoline-2-one derivative is synthesized. All products have the structure 1 H NMR、 13 C NMR, HRMS, melting point and the like. The reaction feeding mode is simple and convenient, and the substrate adaptability is wide.
Has the advantages that:
1) The reaction raw materials are readily available, commercially available or readily prepared.
2) The reaction operation is simple, the intermediate product can be subjected to the next reaction without separation, and the three-component series reaction can be realized.
3) The reaction condition is mild, the reaction can be realized at the temperature near room temperature, the reaction time of most substrates is short, and the efficiency is high.
4) The atom economy is higher, the by-product is only nitrogen and substituted carbonate, the environment is friendly, accord with the requirement of green chemistry better.
5) The substrate adaptability is wide, the yield is excellent, a new quaternary carbon center is constructed at the 3-position of the indoline-2-ketone derivative, particularly when a commercially available chiral phosphine ligand is used, the intermediate enantioselectivity is realized, and the structure of the indoline-2-ketone derivative is greatly enriched. And 3-para aminophenyl and allyl are introduced simultaneously, and the high-activity groups can be conveniently subjected to derivatization reaction to obtain richer indoline-2-one derivatives, which is beneficial to providing a molecular library for subsequent efficient drug screening.
Drawings
FIG. 1 shows 4aaa obtained in example 1 1 H-NMR (nuclear magnetic hydrogen spectrum);
FIG. 2 shows 4aaa obtained in example 1 13 C-NMR (nuclear magnetic carbon spectrum);
FIG. 3 shows HRMS (high resolution Mass Spectrometry) of 4aaa obtained in example 1.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd(OAc) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification afforded 4aaa 86.5mg as a white solid in 81% yield. m.p.121-123 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.32-7.29(m,4H),7.2-7.21(m,12H),7.16-7.12(m,3H),7.04-7.00(m,1H),6.70-6.65(m,3H),5.46-5.35(m,1H),5.07-5.03(m,1H),4.98(d,J＝15.6Hz,1H),4.92-4.89(m,1H),4.75(d,J＝15.6Hz,1H),4.66-4.57(m,4H),3.12-3.07(m,1H),3.01-2.96(m,1H). 13 C NMR(75MHz,CDCl 3 )δ178.8,148.4,143.0,138.6,136.0,133.0,132.2,128.7,128.7,127.9,127.9,127.5,127.5,127.4,127.0,126.7,125.1,122.4,119.1,112.4,109.2,55.8,54.3,43.9,41.9.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 35 N 2 O 535.2744；Found 535.2742.
example 2
Catalyst Rh was added to the reaction tube in sequence 2 (Oct) 4 2.3mg(0.002mmol)，Pd(OAc) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 80.1mg as a white solid in 75% yield.
Example 3
Catalyst Rh was added to the reaction tube in sequence 2 (Opiv) 4 2.3mg(0.002mmol)，Pd(OAc) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL toluene, further adding 1a54.6mg (0.2 mmol) aniline derivative, 2a 79.7mg (0.32 mmol) 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) allyl carbonate derivative and 2mL toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 76.9mg of a white solid in 72% yield.
Example 4
Catalyst Rh was added to the reaction tube in sequence 2 (esp) 2 1.5mg(0.002mmol)，Pd(OAc) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 66.2mg as a white solid in 62% yield.
Example 5
Catalyst Rh was added to the reaction tube in sequence 2 (OAc) 4 0.88mg(0.002mmol)，Pd(OAc) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after the reaction was complete, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 60.8mg as a white solid in a 57% yield.
Example 6
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd(PhCN) 2 Cl 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, and 3a 63.2mg (0.32 mmol) of an allyl carbonate derivative0.4 mmol) and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 42.7mg as a white solid in 40% yield.
Example 7
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd(TFA) 2 2.2mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL toluene, further adding 1a54.6mg (0.2 mmol) aniline derivative, 2a 79.7mg (0.32 mmol) 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) allyl carbonate derivative and 2mL toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification yielded 4aaa 46.0mg as a white solid with a yield of 43%.
Example 8
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 89.7mg as a white solid in 84% yield.
Example 9
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，[Pd(allyl)Cl] 2 2.3mg (0.01 mmol), xantPhos 7mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain whiteSolid 4aaa 71.6mg, yield 67%.
Example 10
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 89.7mg as a white solid in 84% yield.
Example 11
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), davePhos 5.6mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave a white solid, 4aaa, 78.0mg, in 73% yield.
Example 12
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), BINAP 5.6mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 64.1mg as a white solid in 60% yield.
Example 13
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), SPhos 5.6mg (0.012 mmol) 2mL of toluene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of toluene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 83.3mg as a white solid in 78% yield.
Example 14
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added are 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 102.6mg as a white solid in 96% yield.
Example 14-1
Amplification reaction: catalyst Rh was added to a 100mL reaction tube in sequence 2 (PTTL) 4 2.5mg(0.02mmol)，Pd 2 (dba) 3 46mg (0.05 mmol), XPhos 56mg (0.12 mmol) 20mL DCM was added, followed by 1a 0.55g (2 mmol) of the aniline derivative, 2a 0.80g (3.2 mmol) of the 3-diazoindolinone derivative, 3a 0.63g (4 mmol) of the allyl carbonate derivative and 20mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, filtered over celite, washed with ethyl acetate, the mother liquor was collected and the solvent evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aa1.01g as a white solid in 96% yield. Or filtering with diatomite, washing with ethyl acetate, collecting mother liquor, evaporating the solvent under reduced pressure, and recrystallizing with petroleum ether/ethyl acetate (4/1) to obtain 0.908g of product with 85% yield.
Example 15
Sequentially adding catalyst into the reaction tubeRh 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL of xylene, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL of xylene. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after the reaction was complete, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification afforded 4aaa 97.2mg as a white solid in 91% yield.
Example 16
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL tetrahydrofuran, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative, and 2mL tetrahydrofuran. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification yielded a white solid, 4aaa, 32.0mg, with a yield of 30%.
Example 17
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL acetonitrile, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL acetonitrile. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 56.6mg as a white solid in 53% yield.
Example 18
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL of chloroform, and anilineObject 1a54.6mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL of trichloromethane. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification yielded 4aaa 37.4mg as a white solid in 35% yield.
Example 19
Sequentially adding catalyst Pd into the reaction tube 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a54.6mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h without product.
Example 20
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg (0.002 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM and further added are the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h without product.
Example 21
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol) of 2mL of DCM, and further added were 1a54.6mg (0.2 mmol) of the aniline derivative, 2a 79.7mg (0.32 mmol) of the 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of the allyl carbonate derivative and 2mL of DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h without product.
Example 22
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 1.2mg(0.001mmol)，Pd 2 (dba) 3 4.6mg (0.0025 mmol), XPhos 5.6mg (0.006 mmol) 2mL DCM, and further added are 1a54.6mg (0.2 mmol) of the aniline derivative, 2a 79.7mg (0.32 mmol) of the 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of the allyl carbonate derivative and 2mL DCM. Secret keyAnd (5) sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 6h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 96.1mg as a white solid in 90% yield.
Example 23
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 59.8mg (0.24 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 96.1mg as a white solid in 90% yield.
Example 24
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 1mL DCM and further added 1a54.6mg (0.2 mmol) of the aniline derivative, 2a 79.7mg (0.32 mmol) of the 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of the allyl carbonate derivative and 1mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aaa 98.3mg as a white solid in 92% yield.
Example 25
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added are 1a54.6mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.32 mmol) of a 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) of an allyl carbonate derivative and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 25 ℃ for 5h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain white solid 4aaa 97.2mg,the yield thereof was found to be 91%.
Example 26
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a54.6mg (0.2 mmol), 3-diazoindolinone derivative 2b 55.4mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aba 80.7mg, yield 88%; 1 H NMR(400MHz,CDCl 3 )δ7.30-7.19(m,12H),7.15-7.12(m,2H),7.07-7.03(m,1H),6.83-6.81(m,1H),6.64-6.62(m,1H),5.43-5.32(m,1H),5.00-4.97(m,1H),4.89-4.86(m,1H),4.63-4.54(m,4H),3.14(s,3H),2.99-2.92(m,2H). 13 C NMR(100MHz,CDCl 3 )δ178.6,148.3,143.9,138.6,132.9,132.1,128.7,128.0,127.9,127.3,127.0,126.7,125.2,122.3,118.9,112.4,108.1,55.7,54.3,42.0,26.3.HRMS(ESI)m/z:[M+H] + Calcd for C 32 H 31 N 2 O 459.2431；Found 459.2432.
example 27
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2c 75.2mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (Ethyl acetate)) V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aca 89.5mg with the yield of 86 percent; 1 H NMR(400MHz,CDCl 3 )δ7.48-7.44(m,2H),7.36-7.27(m,8H),7.25-7.17(m,9H),7.10-7.07(m,1H),6.82-6.80(m,1H),6.68-6.66(m,2H),5.52-5.42(m,1H),5.10-5.06(m,1H),4.98-4.95(m,1H),δ4.66-4.57(m,4H),3.16-3.10(m,1H),3.02-2.97(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.1,148.4,143.9,138.6,134.8,132.8,132.0,129.,128.7,128.0,127.9,127.9,127.4,127.0,126.8,126.7,125.4,122.8,119.2,112.4,109.4,55.8,54.3,42.4.HRMS(ESI)m/z:[M+H] + Calcd for C 37 H 33 N 2 O 521.2587；Found 521.2587.
example 28
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2d 100.0mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4ada 83.5mg with a yield of 70 percent; 1 H NMR(400MHz,CDCl 3 )δ7.97-7.95(m,1H),7.91-7.89(m,2H),7.32-7.15(m,15H),6.92-6.90(m,2H),6.57-6.55(m,2H),4.98-4.88(m,1H),4.73-4.69(m,1H),4.64-4.55(m,4H),4.50-4.47(m,1H),3.00-2.95(m,1H),2.77-2.72(m,1H),2.35(s,3H). 13 C NMR(100MHz,CDCl 3 )δ177.0,148.7,145.5,139.3,138.4,135.4,131.6,131.2,129.6,128.8,128.7,128.1,127.8,127.1,126.6,126.3,125.4,124.9,119.5,113.8,112.4,56.2,54.3,42.2,21.8.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 35 N 2 O 3 S 599.2363；Found 599.2358.
example 29
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2e 105.0mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aea 100.4mg with a yield of 82 percent; 1 H NMR(400MHz,CDCl 3 )δ7.30-7.27(m,4H),7.23-7.18(m,11H),7.12-7.10(m,1H),7.01-6.96(m,3H),6.67-6.61(m,3H),5.39-5.29(m,1H),5.18-5.13(m,1H),4.95(d,J＝15.6Hz,1H),4.89-4.86(m,1H),4.71(d,J＝15.6Hz,1H),4.64-4.55(m,4H),3.50-3.45(m,1H),3.30-3.25(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.2,148.6,145.3,138.6,135.6,132.6,130.7,129.6,128.7,128.7,127.7,127.7,127.4,127.0,126.8,126.8,125.5,120.4,119.1,112.5,108.1,58.1,54.2,44.1,37.5.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 34 BrN 2 O 613.1849；Found 613.1847.
example 30
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2f 105.0mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after the reaction was complete, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4afa 110.2mg with yield of 90 percent; 1 H NMR(400MHz,CDCl 3 )δ7.33-7.29(m,5H),7.26-7.21(m,12H),7.12-7.10(m,2H),6.78-6.66(m,2H),6.56-6.53(m,1H),5.45-5.34(m,1H),5.09-5.05(m,1H),4.97-4.93(m,2H),4.75-4.70(m,1H),4.67-4.58(m,4H),3.10-3.05(m,1H),2.98-2.93(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.2,148.6,142.1,138.5,135.6,134.6,132.4,130.8,128.8,128.8,128.1,127.8,127.7,127.4,127.0,126.8,126.7,119.7,115.3,112.5,110.7,56.0,54.3,44.0,41.7.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 34 BrN 2 O613.1849；Found 613.1846.
example 31
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2g 84.2mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain white solid of 4aga 93.2mg, the yield is 85 percent, and mp is 148-150 ℃; 1 H NMR(300MHz,CDCl 3 )δ7.32-7.14(m,17H),7.03(s,1H),6.94-6.91(m,1H),6.67-6.64(m,2H),6.58-6.55(m,1H),5.47-5.34(m,1H),5.10-5.04(m,1H),4.98-4.89(m,2H),4.75-4.70(m,1H),4.66-4.55(m,4H),3.13-3.06(m,1H),3.00-2.93(m,1H),2.27(s,3H). 13 C NMR(75MHz,CDCl 3 )δ178.7,148.4,140.6,138.6,136.2,133.1,132.4,131.9,128.7,128.7,128.2,127.9,127.8,127.5,127.4,127.0,126.7,125.8,119.1,112.4,109.0,55.9,54.3,43.9,41.8,21.3.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 549.2900；Found 549.2898.
example 32
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2h 85.5mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aha 103.8mg, and the yield is 94%; 1 H NMR(400MHz,CDCl 3 )δ7.31-7.20(m,15H),7.15-7.12(m,3H),6.71-6.65(m,3H),6.44-6.41(m,1H),5.45-5.34(m,1H),5.02-5.02(m,1H),4.96-4.90(m,2H),4.72-4.68(m,1H),4.65-4.56(m,4H),3.09-3.04(m,1H),2.98-2.93(m,1H). 13 C NMR(100MHz,CDCl 3 )δ179.0,162.7(d,J＝243.1Hz),148.5,144.5(d,J＝11.3Hz),138.5,135.5,132.7,128.8,128.7,127.8,127.7,127.5(d,J＝2.9Hz),127.4,127.2,127.0,126.7,126.1(d,J＝9.5Hz),119.4,112.5,108.6(d,J＝22.0Hz),98.0(d,J＝27.2Hz),55.4,54.3,44.1,42.0. 19 F NMR(282MHz,CDCl 3 )δ-112.3.HRMS(ESI)m/z:[M+H] + Calcd for C 38 H 34 FN 2 O 553.2650；Found 553.2648.
example 33
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a54.6mg (0.2 mmol), 3-diazoindolinone derivative 2i 89.4mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction is carried out for 3h at 30 ℃, and the reaction is reduced after the reaction is finishedThe solvent was evaporated under pressure and the product was chromatographed over silica gel column [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aia 103.8mg, yield 92%; 1 H NMR(400MHz,CDCl 3 )δ7.31-7.27(m,4H),7.24-7.18(m,11H),7.17-7.15(m,2H),7.12-7.10(m,1H),6.66-6.64(m,2H),6.53-6.51(m,1H),6.29-6.29(m,1H),5.47-5.37(m,1H),5.07-5.03(m,1H),4.96-4.89(m,2H),4.72-4.68(m,1H),4.64-4.56(m,4H),3.68(s,3H),3.08-3.03(m,1H),2.98-2.98(m,1H). 13 C NMR(100MHz,CDCl 3 )δ179.3,159.8,148.4,144.3,138.6,136.1,133.2,128.7,127.9,127.6,127.5,127.0,126.7,125.7,124.1,119.1,112.4,106.2,97.3,55.4,55.3,54.3,44.0,42.2.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 2 565.2850；Found 565.2849.
example 34
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were the aniline derivative 1a54.6mg (0.2 mmol), the 3-diazoindolinone derivative 2j 84.2mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after the reaction was complete, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aja 102.0mg with the yield of 93 percent; 1 H NMR(400MHz,CDCl 3 )δ7.30-7.26(m,4H),7.23-7.14(m,11H),7.11-7.08(m,3H),6.96-6.89(m,2H),6.66-6.64(m,2H),5.53-5.42(m,1H),5.19-5.15(m,1H),5.09-5.05(m,2H),4.97-4.94(m,1H),4.64-4.55(m,4H),3.17-3.11(m,1H),3.00-2.94(m,1H),2.23(s,3H). 13 C NMR(100MHz,CDCl 3 )δ179.7,148.3,141.2,138.6,138.0,133.3,132.9,131.9,128.7,128.7,128.1,127.9,127.0,127.0,126.7,125.9,123.2,122.5,119.7,119.1,112.4,55.1,54.3,45.1,42.1,19.0.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 549.2900；Found 549.2898.
example 35
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1b 29.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4baa 62.1mg with the yield of 76 percent; 1 H NMR(400MHz,CDCl 3 )δ7.27-7.21(m,8H),7.18-7.14(m,1H),7.06-7.02(m,1H),6.73-6.71(m,1H),6.52-6.50(m,2H),5.49-5.39(m,1H),5.19-5.05(m,1H),4.97-4.91(m,2H),4.83-4.79(m,1H),3.26-3.22(m,4H),3.13-3.07(m,1H),3.04-3.0(m,1H),1.97-1.94(m,4H). 13 C NMR(100MHz,CDCl 3 )δ178.8,147.2,143.1,136.2,133.1,132.5,128.7,127.9,127.5,127.4,125.2,122.4,119.1,111.8,109.2,55.8,47.7,43.9,42.0,25.6.HRMS(ESI)m/z:[M+H] + Calcd for C 28 H 29 N 2 O 409.2274；Found 409.2273.
example 36
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM and further added are the aniline derivative 1c 36.2mg (0.2 mmol), the 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), the allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction is carried out for 3 hours at 30 ℃, and the reaction is carried out after the reaction is finished and the pressure is reduced to removeSolvent, product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4caa 89.4mg with the yield of 95 percent; 1 H NMR(400MHz,CDCl 3 )δ7.29-7.14(m,9H),7.06-7.02(m,1H),6.73-6.73(m,1H),6.65-6.63(m,2H),5.48-5.38(m,1H),5.09-5.05(m,1H),4.97(d,J＝15.6Hz,1H),4.94-4.91(m,1H),4.79(d,J＝15.6Hz,1H),3.53-3.51(m,8H),3.33(s,6H),3.13-3.08(m,1H),3.03-2.98(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.7,147.0,143.1,136.1,133.0,132.3,128.7,128.0,127.9,127.5,127.4,126.8,125.2,122.4,119.2,111.7,109.2,70.1,59.1,55.7,50.9,43.9,42.0.HRMS(ESI)m/z:[M+H] + Calcd for C 30 H 35 N 2 O 3 471.2642；Found 471.2643.
example 37
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1d 57.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4daa 98.7mg with yield of 90%; 1 H NMR(400MHz,CDCl 3 )δ7.43-7.40(m,3H),7.31-7.29(m,6H),7.25-7.21(m,7H),7.15-7.1(m,1H),6.96-6.91(m,2H),6.78-6.76(m,1H),6.62-6.59(m,1H),6.44-6.43(m,1H),5.38-5.28(m,1H),5.08(d,J＝15.2Hz,1H),5.02-4.98(m,1H),4.88-4.86(m,1H),4.74(d,J＝15.2Hz,1H),4.63-4.54(m,4H),3.08-3.03(m,1H),3.00-2.96(m,1H),1.49(s,3H). 13 C NMR(100MHz,CDCl 3 )δ179.1,148.6,143.2,138.7,138.0,136.2,133.5,132.3,128.7,128.7,128.5,128.2,127.7,127.6,127.0,126.8,126.0,123.6,122.8,119.4,115.8,109.6,108.7,55.6,53.9,44.4,42.9,20.4.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 549.2900；Found 549.2899.
example 38
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1e 60.7mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4eaa 82.4mg with 73 percent of yield; 1 H NMR(400MHz,CDCl 3 )δ7.44-7.42(m,2H),7.34-7.27(m,7H),7.24-7.20(m,7H),7.08-7.04(m,1H),6.91-6.85(m,2H),6.70-6.68(m,1H),6.39-6.36(m,1H),6.12-6.11(m,1H),5.41-5.31(m,1H),5.03-4.94(m,2H),4.90-4.84(m,2H),4.64-4.55(m,4H),3.02(s,3H),2.97-2.96(m,2H). 13 C NMR(100MHz,CDCl 3 )δ179.8,158.1,150.0,143.5,138.7,136.8,134.2,132.4,128.7,128.5,128.1,128.1,127.4,127.1,127.0,126.7,122.7,122.0,119.1,117.7,108.1,104.7,97.7,55.4,54.5,53.3,44.1,41.0.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 2 565.2850；Found 565.2848.
example 39
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added are aniline derivative 1f 66.3mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivativeBio 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4faa 82.9mg, and the yield is 70 percent; 1 H NMR(400MHz,CDCl 3 )δ7.61-7.59(m,1H),7.44-7.42(m,2H),7.34-7.20(m,14H),7.14-7.10(m,1H),6.98-6.92(m,2H),6.86-6.80(m,2H),6.73-6.71(m,1H),5.43-5.32(m,1H),5.26-5.23(m,1H),4.99-4.95(m,1H),4.90-4.87(m,1H),4.69-4.55(m,5H),3.00-2.90(m,5H). 13 C NMR(100MHz,CDCl 3 )δ179.6,169.8,148.1,144.1,137.9,136.6,134.2,133.0,132.3,130.5,128.9,128.6,128.0,127.9,127.5,127.2,126.8,124.0,123.9,122.1,119.5,114.1,112.7,108.6,55.0,53.7,51.8,44.7,43.6.HRMS(ESI)m/z:[M+H] + Calcd for C 40 H 37 N 2 O 3 593.2799；Found 593.2796.
example 40
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and then 1g of 57.4mg (0.2 mmol) aniline derivative, 2a 79.7mg (0.32 mmol) 3-diazoindolinone derivative, 3a 63.2mg (0.4 mmol) allyl carbonate derivative and 2mL DCM were added. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4gaa 62.5mg with the yield of 57 percent; 1 H NMR(400MHz,CDCl 3 )δ7.28-7.15(m,18H),7.06-6.01(m,2H),6.87-6.85(m,1H),6.74-6.72(m,1H),5.43-5.33(m,1H),5.08-5.04(m,1H),4.96(d,J＝15.8Hz,1H),4.93-4.90(m,1H),4.82(d,J＝15.8Hz,1H),4.07-3.99(m,4H),3.13-3.08(m,1H),3.03-2.98(m,1H),2.42(s,3H). 13 C NMR(100MHz,CDCl 3 )δ178.5,149.4,143.0,138.6,136.1,134.4,133.6,132.8,132.1,129.8,128.8,128.7,128.3,128.0,127.6,127.5,127.0,125.3,124.7,122.5,122.1,119.3,109.3,56.7,56.1,44.0,42.1,19.1.HRMS(ESI)m/z:[M+H] + Calcd for C 39 H 37 N 2 O 549.2900；Found 549.2898.
EXAMPLE 41
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a 57.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3b 76.8mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light red oil 4aab 100.4mg with a yield of 82 percent; 1 H NMR(400MHz,CDCl 3 )δ7.32-7.01(m,23H),6.91-6.88(m,2H),6.68-6.60(m,3H),6.45-6.41(m,1H),5.80-5.72(m,1H),5.13(d,J＝15.8Hz,1H),4.66-4.57(m,4H),4.52(d,J＝15.8Hz,1H),3.32-3.27(m,1H),3.15-3.10(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.7,148.5,143.0,138.6,137.2,135.7,134.2,132.1,128.8,128.7,128.5,128.1,127.9,127.7,127.3,127.1,127.0,126.7,126.4,125.1,124.5,122.5,112.5,109.5,56.3,54.3,44.0,41.4.HRMS(ESI)m/z:[M+H] + Calcd for C 44 H 39 N 2 O 611.3057；Found 611.3057.
example 42
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol) of XPhos 5.6mg (0.012 mmol) of 2mL of DCM, and further added with 1a 57.4mg (0.2 mmol) of an aniline derivative, 2a 79.7mg (0.2 mmol) of a 3-diazoindolinone derivative0.32 mmol), the allyl carbonate derivative 3c 88.8mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification gave 4aac 112.7mg of pale red oil, yield 88%; 1 H NMR(400MHz,CDCl 3 )δ7.33-7.19(m,13H),7.14-7.08(m,4H),7.05-7.01(m,3H),6.96-6.92(m,2H),6.76-6.74(m,2H),6.69-6.66(m,2H),6.63-6.60(m,1H),6.40-6.36(m,1H),5.66-5.57(m,1H),5.13(d,J＝15.8Hz,1H),4.67-4.58(m,4H),4.54(d,J＝15.8Hz,1H),3.76(s,3H),3.30-3.24(m,1H),3.14-3.08(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.7,159.0,148.5,143.1,138.6,135.8,133.6,132.2,130.1,128.8,128.7,128.0,128.0,127.7,127.5,127.3,127.1,127.0,126.7,125.1,122.5,122.2,113.9,112.5,109.4,56.4,55.4,54.3,44.0,41.5.HRMS(ESI)m/z:[M+H] + Calcd for C 45 H 41 N 2 O 2 641.3163；Found 641.3163.
example 43
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a 57.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3d 90.4mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purification to obtain light red oil, namely 4aad 92.8mg, with the yield of 72 percent; 1 H NMR(400MHz,CDCl 3 )δ7.32-6.92(m,24H),6.69-6.63(m,3H),6.38-6.34(m,1H),5.75-5.67(m,1H),5.13-5.09(m,1H),4.66-4.51(m,5H),3.31-3.25(m,1H),3.12-3.07(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.6,148.5,143.0,138.5,135.7,135.7,132.9,132.8,132.0,128.7,128.7,128.6,128.1,127.9,127.5,127.5,127.4,127.2,127.0,126.7,125.2,125.1,122.5,112.5,109.4,56.2,54.3,44.0,41.3.HRMS(ESI)m/z:[M+H] + Calcd for C 44 H 38 ClN 2 O 645.2667；Found 645.2665.
example 44
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were aniline derivative 1a 57.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3e 82.4mg (0.4 mmol), and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain white solid 4aae 108.8mg with the yield of 87 percent and mp:113-114 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.32-7.18(m,13H),7.13-6.97(m,7H),6.94-6.89(m,4H),6.90-6.66(m,2H),6.63-6.60(m,1H),6.43-6.38(m,1H),5.81-5.72(m,1H),5.1-5.10(m,1H),4.66-4.52(m,5H),3.32-3.25(m,1H),3.16-3.09(m,1H),2.24(s,3H). 13 C NMR(100MHz,CDCl 3 )δ178.7,148.5,143.0,138.6,138.0,137.1,135.7,134.4,132.1,128.7,128.7,128.4,128.1,128.0,127.9,127.7,127.3,127.2,127.1,127.0,126.7,125.1,124.2,123.4,122.5,112.5,109.4,56.3,54.3,43.9,41.4,21.4.HRMS(ESI)m/z:[M+H] + Calcd for C 45 H 41 N 2 O 625.3213；Found 625.3213.
example 45
Adding catalyst Rh into the reaction tube in turn 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further aniline derivative 1a 57.4mg (0.2 mmol), 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3f 90.4mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after the reaction was complete, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain white solid of 4aaf 96.6mg, the yield is 75%, and mp is 139-140 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.33-7.18(m,13H),7.16-7.02(m,8H),6.98-6.93(m,3H),6.69-6.64(m,3H),6.37-6.33(m,1H),5.81-5.73(m,1H),5.12(d,J＝15.8Hz,1H),4.67-4.58(m,4H),4.55(d,J＝15.8Hz,1H),3.31-3.25(m,1H),3.14-3.09(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.5,148.5,143.0,139.0,138.6,135.7,134.4,133.0,131.9,129.7,128.8,128.7,128.2,127.9,127.5,127.3,127.1,127.0,126.7,126.2,126.2,125.1,124.6,122.6,112.5,109.5,56.1,54.3,44.0,41.3.HRMS(ESI)m/z:[M+H] + Calcd for C 44 H 38 ClN 2 O 645.2667；Found 645.2667.
example 46
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and then 1a 57.4mg (0.2 mmol) of the aniline derivative, 2a 79.7mg (0.32 mmol) of the 3-diazoindolinone derivative, 3g 82.4mg (0.4 mmol) of the allyl carbonate derivative and 2mL DCM were added. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light red solid 4aag 88.7mg with yield of 71 percent and mp:145-146 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.34-7.20(m,13H),7.14-7.0(m,9H),6.92-6.8(m,2H),6.69-6.67(m,2H),6.63-6.61(m,1H),6.57-6.53(m,1H),5.72-5.65(m,1H),5.12-5.08(m,1H),4.67-4.5(m,5H),3.32-3.27(m,1H),3.16-3.10(m,1H),2.07(s,3H). 13 C NMR(100MHz,CDCl 3 )δ178.7,148.5,143.1,138.6,136.5,135.7,135.5,132.6,132.2,130.2,128.8,128.7,128.1,128.0,127.6,127.3,127.2,127.0,126.8,126.0,125.9,125.9,125.2,122.5,112.5,109.5,56.4,54.4,43.9,41.7,19.7.HRMS(ESI)m/z:[M+H] + Calcd for C 45 H 41 N 2 O 625.3213；Found 625.3213.
example 47
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and then 1a 57.4mg (0.2 mmol) of the aniline derivative, 2a 79.7mg (0.32 mmol) of the 3-diazoindolinone derivative, 3h 94.4mg (0.4 mmol) of the allyl carbonate derivative and 2mL DCM were added. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 24h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/10]Purifying to obtain light yellow oil 4aah 113.8mg, and the yield is 87%; 1 H NMR(400MHz,CDCl 3 )δ7.33-7.29(m,4H),7.27-7.18(m,9H),7.15-7.10(m,4H),7.05-6.98(m,3H),6.68-6.62(m,4H),6.60-6.55(m,2H),6.34-6.30(m,1H),5.89(s,2H),5.61-5.54(m,1H),5.13-5.09(m,1H),4.67-4.54(m,5H),3.27-3.22(m,1H),3.12-3.07(m,1H). 13 C NMR(100MHz,CDCl 3 )δ178.7,148.5,147.9,147.0,143.0,138.6,135.8,133.7,132.1,131.8,128.8,128.7,128.1,127.9,127.6,127.4,127.2,127.0,126.7,125.1,122.7,122.5,121.0,112.5,109.4,108.3,105.7,101.0,56.3,54.3,44.0,41.3.HRMS(ESI)m/z:[M+H] + Calcd for C 45 H 39 N 2 O 3 655.2955；Found 655.2954.
example 48
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg(0.005mmol),(R,R)-L 8.2mg(0.012mmol),
MS(100mg),Cs 2 CO 3 (130mg, 0.4 mmol) 2mL of DCE, and then 1a 57.4mg (0.2 mmol) of the aniline derivative, 2b 55.4mg (0.32 mmol) of the 3-diazoindolinone derivative, 3b 76.8mg (0.4 mmol) of the allyl carbonate derivative and 2mL of DCM were added. Sealing and filling argon for reaction. The reaction was carried out at 30 ℃ for 3h, after completion of the reaction, the solvent was evaporated under reduced pressure, and the product was purified by silica gel column chromatography [ eluent: v (ethyl acetate)/V (petroleum ether) =1/7]Purification gave 61.2mg of a white solid, 4abb, 57% yield, 68% enantioselectivity, ee; 1 H NMR(400MHz,CDCl 3 )δ7.31-7.03(m,20H),6.81-6.79(m,1H),6.67-6.64(m,2H),6.34-6.30(m,1H),5.81-5.74(m,1H),4.65-4.56(m,4H),3.15-3.03(m,5H). 13 C NMR(100MHz,CDCl 3 ) δ 178.6,148.4,143.9,138.6,137.4,133.8,128.7,128.5,128.1,128.0,127.2, 127.0,126.7,126.2,125.4,124.6,122.4,112.4,108.2,56.1,54.3,41.3,26.4.Hplc (IA, I-PrOH/n-hexane =30/70, flow =1.0mL/min, I =215 nm) t R ＝8.69min(major),12.02min(minor),68％ee.[α] D 25 :59.4°(c:0.1,CHCl 3 ).
Comparative example 1
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM, and further added were 61.4mg (0.2 mmol) of N, N-dibenzyl-2-chloroaniline, 3-diazoindolinone derivative 2a 79.7mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction is carried out for 24 hours at the temperature of 30 ℃, one equivalent of N, N-dibenzyl-2-chloroaniline is converted by 30 percent, and the yield of the target product is less than 5 percent.
Comparative example 2
Catalyst Rh was added to the reaction tube in sequence 2 (PTTL) 4 2.5mg(0.002mmol)，Pd 2 (dba) 3 4.6mg (0.005 mmol), XPhos 5.6mg (0.012 mmol) 2mL DCM was added, 54.6mg (0.2 mmol) of N, N-dibenzylaniline, 1-benzyl-3-diazo-7-nitroindol-2-one 942mg (0.32 mmol), allyl carbonate derivative 3a 63.2mg (0.4 mmol) and 2mL DCM. Sealing and filling argon for reaction. The reaction is carried out for 24 hours at the temperature of 30 ℃, one equivalent of N, N-dibenzyl-2-chloroaniline is converted by 40 percent, and the yield of the target product is less than 20 percent.
Claims (10)
1. The method for synthesizing the 3-tetra-substituted indoline-2-ketone compound by the one-pot method is characterized by comprising the following steps: a method for realizing the dual functionalization of the 3-diazoindoline-2-ketone derivative by the double catalysis of Rh/Pd on aniline derivatives and allyl carbonate;
the specific reaction is as follows:
firstly, adding a rhodium catalyst, a palladium catalyst and a phosphine ligand into the reaction mixture, then adding a solvent into the reaction mixture, adding an aniline derivative, a 3-diazoindoline-2-one derivative and an allyl carbonate derivative into the reaction mixture under the protection of argon, and reacting to obtain a target product;
wherein R is 1 Is benzyl, methyl, phenyl, p-toluenesulfonyl; r 2 Is hydrogen, 4-bromine, 5-methyl, 6-fluorine, 6-methoxyl or 7-methyl; (R) 3 ) 2 Is dibenzyl, 1,4-butylidene or bis (2-methoxyethyl); r 4 Is hydrogen, 3-methyl, 3-methoxy, 3-methoxycarbonyl, 2-methyl; r 5 Is hydrogen, phenyl, 4-methoxyphenyl, 4-chlorophenyl, 3-methylphenyl, 3-chlorophenyl, 2-methylphenyl, piperonyl-4-yl.
2. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the aniline derivative comprises the following structural formula:
3. the method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, comprising the following steps: the 3-diazoindoline-2-ketone derivative comprises the following structural formula:
4. the method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the allyl carbonate derivative comprises the following structural formula:
5. the method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the dosage of the diazo compound is 1 to 2 equivalents of the dosage of the aniline derivative, and the dosage of the allyl carbonate derivative is 1 to 2 equivalents of the dosage of the aniline derivative.
6. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the rhodium catalyst is Rh 2 (OAc) 4 、Rh 2 (PTTL) 4 、Rh 2 (Oct) 4 、Rh 2 (esp) 2 、Rh 2 (OPiv) 4 The using amount is 1 to 2 percent of the mole number of the aniline derivative; the palladium catalyst is Pd (OAc) 2 、Pd(PhCN) 2 Cl 2 、Pd(TFA) 2 、Pd 2 (dba) 3 、Pd[(allyl)Cl] 2 The dosage is 1 to 5 percent of the mole number of the aniline derivative.
7. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the phosphine ligand is Xantphos, XPhos, davePhos, BINAP, SPhos,
8. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the solvent is one of toluene, xylene, tetrahydrofuran, trichloromethane, acetonitrile and dichloromethane; the concentration of the aniline derivative in the solvent is 0.05-0.2 mol/L.
9. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, wherein: the specific reaction temperature is 20-35 ℃.
10. The method for synthesizing 3-tetrasubstituted indoline-2-one compounds according to claim 1, comprising the following steps: the specific reaction time is 3 to 36 hours.
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