CN110357848B - Ruthenium-catalyzed synthesis method of 3-substituted isocoumarin - Google Patents
Ruthenium-catalyzed synthesis method of 3-substituted isocoumarin Download PDFInfo
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Abstract
The invention discloses a synthesis method of ruthenium-catalyzed 3-substituted isocoumarin, which takes ruthenium as a catalyst, realizes the activation of carbon-hydrogen bonds at the ortho position of aromatic hydrocarbon and intramolecular ring closure reaction under the guiding action of weak coordination oxygen atoms, and synthesizes a plurality of 3-substituted isocoumarin compounds in one step with high efficiency through simple operation.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to a synthesis method of ruthenium-catalyzed 3-substituted isocoumarin.
Background
Isocoumarins are basic building blocks in many natural products, drugs and biologically active compounds. A large amount of isocoumarins have been isolated from natural products, and particularly 3-substituted isocoumarins have remarkable specific effects in the aspect of medicines, such as anti-tumor, anti-inflammatory, antibacterial and anti-AIDS. In addition, isocoumarins are valuable synthetic intermediates, which can be functionally modified to synthesize interesting molecules, such as anesin, isochromenes, alkaloids, etc. In view of the wide applicability of isocoumarins, scientists have made great and long-lasting efforts to find efficient methods to synthesize isocoumarins.
The traditional method for synthesizing isocoumarin mainly depends on electrophilic cyclization reaction of substituted aromatic alkyne and coupling reaction of terminal alkyne and 2-halogenated aromatic acid/ester promoted by transition metal. However, most of these methods have problems of high degree of functionalization of starting materials, formation of product isomeric mixture, multi-step synthesis (multi-step), etc., and limit the practicality of the synthesis.
Therefore, it is an urgent problem to develop a novel, mild, direct and rapid method for synthesizing isocoumarin to provide its utility.
Disclosure of Invention
In view of the above, the invention discloses a ruthenium-catalyzed synthesis method of 3-substituted isocoumarin, which at least solves the problems of multiple synthesis steps, complex process, high cost, low practicability and the like in the synthesis of isocoumarin in the prior art.
The technical scheme provided by the invention is specifically a ruthenium-catalyzed synthesis method of 3-substituted isocoumarin, which comprises the following steps:
placing a reactor in inert gas, sequentially adding alpha-carbonyl sulfide ylide, a catalyst, a silver salt, an additive and a solvent, and stirring for reaction at the temperature of 80-120 ℃;
after the reaction is finished, extracting and adjusting the solvent by using a rotary evaporator, and carrying out column chromatography on the crude product to obtain a product;
the catalyst is a ruthenium catalyst.
Preferably, the α -carbonylthioylide has the following general structural formula:
wherein, R is one or more of C1-C8 alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I.
Further preferably, the ruthenium catalyst is [ Ru (p-cymene) Cl2]2。
More preferably, the amount of the ruthenium catalyst used is 5% times the amount of the α -carbonylthio ylide.
Further preferably, the silver salt is AgNO3、AgSbF6、Ag2CO3AgOAc and CF3CO2One or more of Ag.
More preferably, the amount of the silver salt is 20% times the amount of the α -carbonylthioylide.
Further preferably, the additive is AdCO2H、AcOH、MesCO2H、2,4-Me2PhCOOH、PivOH、Zn(OTf)2And Cu (OAc)2·H2One or more of O.
More preferably, the amount of the additive is 1 time the amount of the alpha-carbonylsulfide ylide.
Further preferably, the solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydrofuran, trifluoroethanol, ethanol, and hexafluoroisopropanol.
Further preferably, the solvent is used in an amount of: 0.5-10 ml of solvent is used for each millimole of reactant alpha-carbonyl sulfur ylide.
The ruthenium-catalyzed synthesis method of the 3-substituted isocoumarin, disclosed by the invention, takes ruthenium as a catalyst, and realizes the activation of the carbon-hydrogen bond at the ortho position of the aromatic hydrocarbon and the intramolecular ring closure reaction under the guiding action of the weakly coordinated oxygen atom, so that various 3-substituted isocoumarin compounds are efficiently synthesized in one step through simple operation, the raw materials of the reactants are cheap and easy to obtain, the reaction steps are few, the operation is simple, and the step economy and the market economy are realized.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a hydrogen spectrum of Compound 2a of example 1 of the present disclosure;
FIG. 2 is a carbon spectrum of Compound 2a of example 1 of the present disclosure;
FIG. 3 is a hydrogen spectrum of Compound 2b of example 2 of the present disclosure;
FIG. 4 is a carbon spectrum of Compound 2b of example 2 of the present disclosure;
FIG. 5 is a hydrogen spectrum of Compound 2c of example 3 of the present disclosure;
FIG. 6 is a carbon spectrum of Compound 2c of example 3 of the present disclosure;
FIG. 7 is a hydrogen spectrum of Compound 2d of example 4 of the present disclosure;
FIG. 8 is a carbon spectrum of Compound 2d of example 4 of the present disclosure;
FIG. 9 is a hydrogen spectrum of Compound 2e of example 5 of the present disclosure;
FIG. 10 is a carbon spectrum of Compound 2e of example 5 of the present disclosure.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of methods consistent with certain aspects of the invention, as detailed in the appended claims.
The embodiment provides a synthesis method of ruthenium-catalyzed 3-substituted isocoumarin, which comprises the following specific synthesis processes:
placing a reactor in inert gas, sequentially adding alpha-carbonyl sulfide ylide, a catalyst, a silver salt, an additive and a solvent, and stirring for reaction at the temperature of 80-120 ℃;
after the reaction is finished, extracting and adjusting the solvent by using a rotary evaporator, and carrying out column chromatography on the crude product to obtain a product;
the catalyst is a ruthenium catalyst.
Wherein, the inert gas can be selected from nitrogen or argon, and the eluent adopted in the column chromatography is a mixed solvent of petroleum ether and ethyl acetate.
The corresponding reaction formula of the synthesis method is as follows:
a large number of experiments prove that: the alpha-carbonyl sulfide ylide has the following structural general formula:
and R is one or more of C1-C8 alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I; the ruthenium catalyst can be [ Ru (p-cymene) Cl2]2And the dosage of the ruthenium catalyst is 5 percent times of the dosage of the alpha-carbonyl sulfur ylide; the silver salt can be AgNO3、AgSbF6、Ag2CO3AgOAc and CF3CO2One or more Ag, and the dosage of the silver salt is 20% times of the dosage of the alpha-carbonyl sulfide ylide; AdCO is selected as additive2H、AcOH、MesCO2H、2,4-Me2PhCOOH、PivOH、Zn(OTf)2And Cu (OAc)2·H2One or more of O, and the dosage of the additive is 1 time of the dosage of the alpha-carbonyl sulfide ylide; the solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydrofuran, trifluoroethanol, ethanol and hexafluoroisopropanol, and the solvent is 0.5-10 ml for each millimole of the reactant alpha-carbonyl sulfide ylide.
The 3-substituted isocoumarin synthesized by the method has the following structural general formula:
wherein the content of the first and second substances,
r is one or more of C1-C8 alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
the heteroaryl is one or more of pyridyl, thienyl and furyl.
The invention is further illustrated by the following specific examples.
Example 1
The reactor was placed under nitrogen and 0.40mmol (78.4mg) of α -carbonylthioylide (1a), 0.02mmol (12.2mg) of [ Ru (p-cymene) Cl were added in succession2]2，0.08mmol(27.5mg)AgSbF60.40mmol (24.0mg) of AcOH, 2mL of TFE, and stirring at 100 ℃ for 12 h. After the reaction is finished, the solvent is extracted and adjusted by a rotary evaporator, the crude product is subjected to column chromatography, and the eluent is a mixed solvent of petroleum ether and ethyl acetate, so that 40.5mg of 3-substituted isocoumarin 2a is obtained, and the separation yield is 91%.
Referring to fig. 1 and 2, the characterization data for compound 2a is as follows:
1H NMR(400MHz,CDCl3)δ8.29(d,J＝8.4Hz,1H),7.87(dd,J＝8.0,1.6Hz,2H),7.72-7.68(m,1H),7.50-7.40(m,5H),6.94(s,1H).13C NMR(100MHz,CDCl3)δ162.3,153.6,137.5,134.9,132.0,130.0,129.6,128.8,128.2,126.0,125.2,120.5,101.8。
example 2
The reactor was placed under nitrogen and 0.40mmol (84.0mg) of α -carbonylthioylide (1b), 0.02mmol (12.2mg) of [ Ru (p-cymene) Cl were added in succession2]2，0.08mmol(27.5mg)AgSbF60.40mmol (24.0mg) of AcOH, 2mL of TFE, and stirring at 100 ℃ for 12 h. After the reaction is finished, the solvent is extracted and adjusted by a rotary evaporator, the crude product is subjected to column chromatography, and an eluent is a mixed solvent of petroleum ether and ethyl acetate, so that 45.0mg of 3-substituted isocoumarin 2b is obtained, and the separation yield is 90%.
Referring to fig. 3 and 4, the characterization data for compound 2b is as follows:
1H NMR(400MHz,CDCl3)δ8.17(d,J＝8.0Hz,1H),7.76(d,J＝8.4Hz,2H),7.29-7.24(m,4H),6.83(s,1H),2.47(s,3H),2.40(s,3H).13C NMR(100MHz,CDCl3)δ162.5,153.9,145.9,140.2,137.8,129.6,129.5,129.4,129.3,125.8,125.1,118.0,101.1,22.0,21.4。
example 3
The reactor was placed under nitrogen and 0.40mmol (92.0mg) of α -carbonylthioylide (1c), 0.02mmol (12.2mg) of [ Ru (p-cymene) Cl2]2，0.08mmol(27.5mg)AgSbF60.40mmol (24.0mg) of AcOH, 2mL of TFE, and stirring at 100 ℃ for 12 h. After the reaction is finished, the solvent is extracted and adjusted by a rotary evaporator, the crude product is subjected to column chromatography, and an eluent is a mixed solvent of petroleum ether and ethyl acetate, so that 48.9mg of 3-substituted isocoumarin 2c is obtained, and the separation yield is 84%.
Referring to fig. 5, 6, characterization data for compound 2c are as follows:
1H NMR(400MHz,CDCl3)δ8.23(d,J＝8.4Hz,1H),7.81(d,J＝8.4Hz,2H),7.49-7.44(m,4H),6.86(s,1H).13C NMR(100MHz,CDCl3)δ161.2,153.8,141.7,138.7,136.5,131.4,130.0,129.2,128.9,126.6,125.5,118.8,101.0。
example 4
The reactor was placed under nitrogen and 0.40mmol (85.6mg) of α -carbonylthioylide (1d), 0.02mmol (12.2mg) of [ Ru (p-cymene) Cl were added in succession2]2，0.08mmol(27.5mg)AgSbF60.40mmol (24.0mg) of AcOH, 2mL of TFE, and stirring at 100 ℃ for 12 h. After the reaction is finished, the solvent is extracted and adjusted by a rotary evaporator, the crude product is subjected to column chromatography, and the eluent is a mixed solvent of petroleum ether and ethyl acetate, so that 41.2mg of 3-substituted isocoumarin 2d is obtained, and the separation yield is 80%.
Referring to fig. 7, 8, characterization data for compound 2d is as follows:
1H NMR(400MHz,CDCl3)δ8.10(dd,J＝7.0,2.0Hz,1H),7.67(d,J＝8.0Hz,1H),7.61-7.57(m,1H),7.49-7.41(m,3H),7.16-7.11(m,2H).13C NMR(100MHz,CDCl3)δ163.1(d,J＝245.3Hz),160.6(d,J＝3.6Hz),157.3(d,J＝251.5Hz),152.8(d,J＝4.0Hz),133.8(d,J＝8.1Hz),130.5(d,J＝8.2Hz),128.9(d,J＝7.7Hz),126.3(d,J＝16.7Hz),125.4(d,J＝3.9Hz),122.0(d,J＝3.8Hz),121.0(d,J＝3.1Hz),120.4(d,J＝19.6Hz),117.2(d,J＝21.2Hz),112.4(d,J＝23.8Hz),95.1(d,J＝5.0Hz)。
example 5
The reactor was placed under nitrogen and 0.40mmol (85.6mg) of α -carbonylthioylide (1e), 0.02mmol (12.2mg) of [ Ru (p-cymene) Cl were added in succession2]2，0.08mmol(27.5mg)AgSbF60.40mmol (24.0mg) of AcOH, 2mL of TFE, and stirring at 100 ℃ for 12 h. After the reaction is finished, the solvent is pumped and adjusted by a rotary evaporator, the crude product is subjected to column chromatography, and the eluent is a mixed solvent of petroleum ether and ethyl acetate, so that 42.7mg of 3-substituted isocoumarin 2e is obtained, and the separation yield is 76%.
Referring to fig. 9, 10, characterization data for compound 2e is as follows:
1H NMR(400MHz,CDCl3)δ1H NMR(400MHz,Chloroform-d)δ7.98(dd,J＝7.6,1.6Hz,1H),7.59(dd,J＝8.4,7.6Hz,1H),7.38-7.28(m,1H),7.28(s,1H),7.07-7.02(m,2H),6.98(d,J＝8.4Hz,1H),6.92(d,J＝8.0Hz,1H),4.01(s,3H),3.95(s,3H).13C NMR(100MHz,CDCl3)δ161.5,159.4,157.2,150.7,141.0,135.5,130.7,128.9,120.8,120.6,118.5,111.3,109.7,109.4,107.0,56.3,55.6。
the following series of experiments were carried out with only partial conversion of the components and ratios based on the following reaction formula, as shown in Table 1, wherein the reactants 1a (0.4mmol), [ Ru (p-cymene) Cl2]2(5 mol%), silver salt-Ag salt, additive-additive (0.4mmol), TFE (2 m)L), and reacting for 12h under a nitrogen environment. In example 13 [ Ru (p-cymene) Cl2]2(2.5mol％)，AgSbF6(10mol％)
Table 1:
the following series of experiments were carried out with only partial conversion of the components and ratios based on the following reaction formula, as shown in Table 1, wherein the reactants 1a (0.4mmol), [ Ru (p-cymene) Cl2]2(5mol％),AgSbF6(20 mol%), Additive-Additive (0.4mmol), solvent-solvent (2mL) under nitrogen for 12h, example 29 using [ RhCp. Cl ]2]2(5.0 mol%) as catalyst.
Note: trace represents the detection of trace amounts of the target product.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (5)
1. A ruthenium-catalyzed synthesis method of 3-substituted isocoumarin is characterized by comprising the following steps:
placing a reactor in inert gas, sequentially adding alpha-carbonyl sulfide ylide, a catalyst, a silver salt, an additive and a solvent, and stirring for reaction at the temperature of 80-120 ℃;
after the reaction is finished, extracting and adjusting the solvent by using a rotary evaporator, and carrying out column chromatography on the crude product to obtain a product;
the catalyst is a ruthenium catalyst;
the alpha-carbonyl sulfur ylide has the following structural general formula:
wherein R is one or more of C1-C8 alkyl, alkoxy, trifluoromethyl, cyano, nitro, F, Cl, Br and I;
the ruthenium catalyst is [ Ru (p-cymene) Cl2]2；
The silver salt is AgNO3、AgSbF6、Ag2CO3AgOAc and CF3CO2One or more of Ag;
the additive is AdCO2H、AcOH、MesCO2H、2,4-Me2PhCOOH、PivOH、Zn(OTf)2And Cu (OAc)2·H2One or more of O;
the solvent is one or more of N, N-dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, 1, 4-dioxane, 1, 2-dichloroethane, tetrahydrofuran, trifluoroethanol, ethanol and hexafluoroisopropanol.
2. The ruthenium-catalyzed process for the synthesis of 3-substituted isocoumarins according to claim 1, wherein the amount of the ruthenium catalyst is 5% of the amount of the α -carbonylthioylide.
3. The ruthenium-catalyzed process for the synthesis of 3-substituted isocoumarins according to claim 1, wherein the amount of silver salt is 20% of the amount of the α -carbonylthioylide.
4. The ruthenium-catalyzed process for the synthesis of 3-substituted isocoumarins according to claim 1, wherein the amount of the additive is 1-fold the amount of the α -carbonylthioylide.
5. The ruthenium-catalyzed process for the synthesis of 3-substituted isocoumarins according to claim 1, wherein the solvent is used in an amount of: 0.5-10 ml of solvent is used for each millimole of reactant alpha-carbonyl sulfur ylide.
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| Cp*Co(III)-Catalyzed C−H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors;Shuying Ji et al.;《Org. Lett.》;20180912;第20卷;5981-5984 * |
| Rhodium(III)-catalyzed chemodivergent annulations betweenN-methoxybenzamides and sulfoxonium ylidesviaC–H activation;Youwei Xu et al.;《Chem. Commun.》;20180105;第54卷;670-673 * |
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