CN110305156B - A kind of alkyne derivative containing nitrogen-oxygen bond and its preparation method and application - Google Patents

Abstract

The present invention belongs to an organic synthesis technologyThe technical field, in particular to an alkyne derivative containing a nitrogen-oxygen bond and a preparation method and application thereof. The invention provides an alkyne derivative containing a nitrogen-oxygen bond, which has a structural formula shown in formula (I), wherein R¹And R²Independently selected from hydrogen, alkyl of C1-C20, aryl of C5-C30, substituted aryl of C5-C30 or aromatic heterocyclic radical of C5-C30, R³To replace silicon base. In the invention, the alkyne derivative containing the nitrogen-oxygen bond contains an easily-converted nitrogen-oxygen bond, and primary amine with high added value and polysubstituted alcohol compounds containing alkynyl can be obtained by reduction, so that the alkyne derivative has good application prospect in the field of organic synthesis; in addition, the alkyne derivative containing the nitrogen-oxygen bond contains silicon base which is directly connected with alkyne and can be conveniently detached, and a terminal alkyne compound can be further obtained.

Description

A kind of alkyne derivative containing nitrogen-oxygen bond and its preparation method and application

technical field

The invention belongs to the technical field of organic synthesis, and in particular relates to a nitrogen-oxygen bond-containing alkyne derivative and a preparation method and application thereof.

Background technique

Alkynes have unique physical properties such as rigidity, optical properties and rich chemical properties such as simple and efficient electrophilic addition, nucleophilic addition, Diels-Alder reaction to build molecular complexity, and alkynes can also be achieved through click reactions ( Click reaction) to quickly and reliably complete the chemical synthesis of various molecules. Although alkynes are ubiquitous functional groups in materials, medicine and other fields. However, the existing alkyne synthesis methods mainly rely on transition metal-catalyzed coupling reaction of terminal alkynes to construct Csp ² -Csp bonds, that is, most of them still focus on alkenes, aromatic substituted alkynes;

The construction of alkyl-substituted terminal alkynes in the prior art is still an important challenge in the field of organic synthesis:

1) If the strategy of reacting an alkyl halide with an alkynylating agent is directly used to construct an internal alkyne with both alkyl groups at both ends, the metal alkyl catalyst species usually generated in situ from the alkyl halide are more prone to rapid catalysis. The β-H elimination reaction results in olefin by-products, making it difficult to obtain the target conversion;

2) If the strategy of reacting alkyl carbon-hydrogen bonds with alkynylation reagents is directly used to construct alkyl-substituted terminal alkynes, this strategy has good step economy and atom economy. However, considering that the activity of alkyl Csp ³ -H bonds is very low, and alkyl substrates usually contain multiple different kinds of alkyl Csp ³ -H bonds, this also makes it possible to explore the direct response to alkyl Csp ³ -H bonds The direct position-selective alkynylation of alkynyls remains a great challenge.

Examples of prior art construction of alkynes from simple alkyl Csp ³ -H bonds through Csp ³ -H bond-selective functional group strategies are very limited and focus on the use of difficult-to-transform, or/and expensive radicals. The functional group synthesized by the group, such as the amide of 4-trifluoromethyl-2,3,5,6-tetrafluoroaniline, the amide derivative of 8-aminoquinoline as the guiding group to promote the selective alkyne of Csp ³ -H bond base reaction. Despite its good catalytic efficiency, the difficult conversion or availability of directing groups limits its wide application.

In summary, the efficient synthesis of alkyl alkynes, especially alkyne compounds containing easily convertible functional groups, still needs to be further developed. At present, the types of alkyne derivatives are limited and need to be expanded.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a nitrogen-oxygen bond-containing alkyne derivative and a preparation method and application thereof, which are used to provide a new nitrogen-oxygen bond-containing alkyne derivative, broaden the nitrogen-oxygen bond-containing alkyne derivative Types of hydrocarbon derivatives.

The concrete technical scheme of the present invention is as follows:

A nitrogen-oxygen bond-containing alkyne derivative, the structural formula of the nitrogen-oxygen bond-containing alkyne derivative is shown in formula (I):

Wherein, R ¹ and R ² are independently selected from hydrogen, C1-C20 hydrocarbon group, C5-C30 aryl group, C5-C30 substituted aryl group or C5-C30 aromatic heterocyclic group, and R ³ is a substituted silicon group.

The nitrogen-oxygen bond-containing alkyne derivatives of the invention contain easily convertible nitrogen-oxygen bonds, can obtain high value-added primary amines and alkynyl-containing polysubstituted alcohol compounds through reduction, and have good application in the field of organic synthesis prospect. In addition, the alkyne derivative containing nitrogen-oxygen bond of the present invention contains a silicon group which is directly connected with the carbon-carbon triple bond of the alkyne and can be easily left, and can further obtain a terminal alkyne compound.

In the present invention, the alkyne derivatives containing nitrogen-oxygen bonds can be easily converted into alcohol compounds containing alkynyl groups, such as through LAH (lithium aluminum hydride) reduction and TBAF (tetrabutylammonium fluoride) desiliconization, which can be quantitatively to obtain the alkynyl-containing alcohol target product.

Preferably, R ¹ and R ² are independently selected from hydrogen, alkyl, cycloalkyl, phenyl, substituted phenyl, naphthyl, furanyl, thienyl, indolyl or pyrrolyl, and R ³ is selected from triiso propylsilyl, dimethyl-tert-butylsilyl or cyclohexyl-containing oxysilyl ether.

Further, R ¹ and R ² are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, benzyl, phenethyl, phenylpropyl, phenyl, naphthyl, furyl , thienyl, indolyl or pyrrolyl, R ³ is selected from triisopropylsilyl (-TIPS), dimethyl tert-butylsilyl (-TMS) or cyclohexyl-containing oxysilyl ether.

Further, R ¹ and R ² are independently selected from hydrogen, methyl, ethyl, benzyl, 4-fluoro-benzyl, 2-chlorobenzyl, 2-bromobenzyl or phenethyl, and R ³ is Triisopropylsilyl (-TIPS).

Preferably, the nitrogen-oxygen bond-containing alkyne derivative represented by formula (I) is selected from

The present invention also provides a method for preparing a nitrogen-oxygen bond-containing alkyne derivative, comprising the following steps:

The compound represented by the formula (II) and the compound represented by the formula (III) are reacted under a catalyst to obtain the nitrogen-oxygen bond-containing alkyne derivative represented by the formula (I);

in,

R ¹ and R ² are independently selected from hydrogen, C1-C20 hydrocarbon group, C5-C30 aryl group, C5-C30 substituted aryl group or C5-C30 aromatic heterocyclic group, R ³ is substituted silicon group, X is hydrogen, bromine, chlorine, iodine or an iodine-containing heterocyclic group, the iodine-containing heterocyclic group is preferably

The catalyst is a metal catalyst, and the metal of the metal catalyst is selected from one or more of palladium, ruthenium, rhodium and iridium.

Existing alkyne synthesis methods mainly rely on transition metal-catalyzed coupling reaction of terminal alkynes to construct Csp ² -Csp bonds, so that the products are concentrated in alkenes and aromatic substituted alkyne compounds. Based on simple and readily available substrates, it is still a great challenge to rapidly construct alkyne derivatives containing nitrogen-oxygen bonds with important synthetic value through efficient synthetic strategies. The reasons are: 1) Sonogashira reaction starting from alkyl halide often faces the Csp ³ -metal bond generated in situ and is prone to rapid β-H elimination to obtain alkene compounds; 2) If you start directly with alkyl Csp ³ -H bond The construction of alkynes, despite their excellent step economics, is extremely challenging for this type of reaction. On the one hand, the relatively flexible alkyl Csp3 ^- H bond has high bond energy, which enables activation of this inert chemical bond It is very difficult; it should also be pointed out that for a specific nitrogen-oxygen bond-containing alkyl compound, it often contains a large number and a complex variety of Csp ³ -H bonds, which makes the activation of a specific Csp ³ -H bond It is extremely challenging; more importantly, the alkyl compounds containing nitrogen-oxygen bonds are prone to oxidation (becoming ketones, aldehydes or carboxylic acids, etc.), elimination (becoming isomers of olefins) under oxidative or basic conditions. The selective functionalization of direct Csp ³ -H bonds of alkyl alcohols catalyzed by transition metals is still a major challenge in the field of organic synthesis.

In order to achieve the reactivity and selectivity of inert alkyl Csp ³ -H bond functionalization reactions, currently, targeting strategies are widely used in the selective functionalization of inert C-H bonds. However, common directing groups (such as Professor Yu Jinquan of Scripps Research Institute in the United States used polyfluoroaniline-substituted amide compounds as guiding groups, and Professor Chatani of Osaka University in Japan used amides derived from 8-aminoquinoline as guiding groups) promoted direct alkanes. However, such ^directing groups are often difficult to convert or expensive, which also makes the whole reaction process difficult to achieve practical application.

Even more challenging, for direct Csp3 ^- H alkynylation of nitrogen-oxygen bond-containing alkyl compounds, transition metal catalysis is extremely difficult due to alkynylation reagents such as terminal alkynes or functionalized alkynes. The Glaser reaction is prone to give conjugated diacetylene side reactions, which greatly reduces the occurrence of the target conversion.

In the present invention, the compound represented by the formula (II) and the compound represented by the formula (III) are reacted under the action of a catalyst to obtain the nitrogen-oxygen bond-containing alkyne derivative represented by the formula (I), which can efficiently and selectively The Csp ³ -H bond of the compound represented by formula (II) is subjected to alkynylation reaction. In addition, the compounds represented by the formula (II) and the compounds represented by the formula (III) are widely present in the fields of medicine and materials, and the raw materials are common and readily available, and the obtained nitrogen-oxygen bond-containing alkyne derivatives contain easily convertible nitrogen-oxygen bonds. , high value-added primary amines and alkynyl-containing polysubstituted alcohol compounds can be obtained by reduction, which has good application prospects in the field of organic synthesis.

The preparation method of the present invention is based on metal catalysis, and directly performs Csp ³ -H bond alkynylation reaction on alkyl compounds containing nitrogen-oxygen bonds, and has the following characteristics: 1) The preparation method of the present invention directly starts from inert Csp ³ -H bonds to construct alkynes Hydrocarbons have good atom economy, step economy, and conform to the synthetic concept of green chemistry; 2) As a substituent of alkynes, silicon group can be easily removed to obtain terminal alkynes; 3) The product contains nitrogen-oxygen bonds The alkyne derivatives of the present invention contain easily convertible nitrogen-oxygen bonds, which can further realize the efficient synthesis of primary amines and polysubstituted alkynyl-containing alcohol compounds; 4) The chemical conversion of the preparation method of the present invention has excellent positional specificity. Oneness, that is, the reaction generates nitrogen-containing organometallic cyclic intermediates in situ, and then performs regioselective alkynylation on the primary Csp ³ -H bond to obtain nitrogen-oxygen bond-containing alkyne derivatives.

The preparation method of the invention is based on the nitrogen-oxygen bond of the nitrogen-oxygen bond-containing alkyl compound, which has the advantages of easy introduction, easy conversion, etc., and avoids elimination and oxidation side reactions that are easy to occur in the catalytic oxidation of carbon-hydrogen bond functionalization reaction, thereby obtaining carbonyl It not only solves the side reactions such as oxidation and elimination of nitrogen-oxygen bond-containing alkyl compounds, but also provides a simple and efficient strategy for Csp ³ -H of nitrogen-oxygen bond-containing alkyne compounds. key for efficient conversion. The nitrogen-oxygen bond in the nitrogen-oxygen bond-containing alkyne derivative obtained by the preparation method of the present invention can be converted into an alkynyl group-containing alcohol compound and a primary amine through a reduction reaction, so that the nitrogen-oxygen bond-containing alkyl compound can be converted into a nitrogen-oxygen bond-containing alkyl compound. Alkynyl alcohols, nitroxide bonds as traceless directing groups. The preparation method of the present invention can realize the transformation through the adjustment of the nitrogen-oxygen bond structure to achieve the position-selective alkynylation reaction of the Csp ³ -H bond through the five-membered metal cyclic intermediate containing nitrogen atoms; and the transformation Reacts only to the primary Csp ³ -H bond.

The preparation method of the invention has a wide range of application to substrates, the obtained position-selective nitrogen-oxygen bond-containing alkyne derivatives are easy to be converted later, and late-stage modification of alcohol derivatives with potential biological activity can be directly carried out.

In the present invention, the metal catalyst is more preferably a metal catalyst whose metal is divalent ruthenium or trivalent rhodium.

Preferably, the reaction of the compound represented by the formula (II) and the compound represented by the formula (III) is specifically:

The compound represented by the formula (II) and the compound represented by the formula (III) are dissolved in an inert solvent, and the reaction is carried out under basic conditions under the action of an oxidant and a metal catalyst.

Preferably, the metal catalyst is selected from palladium acetate (Pd(OAc) ₂ ), palladium chloride (PdCl ₂ ), ruthenium trichloride (RuCl ₃ ), dichloro(p-methylisopropylphenyl)ruthenium ( II) dimer ([Ru(p-cymene)Cl ₂ ] ₂ ), dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer ([Cp*RhCl ₂ ] ₂ ), pentamethylcyclopentadienyl Methylcyclopentadienyltriacetonitrile-bis(hexafluoroantimonate)rhodium ([Cp*Rh(MeCN) ₃ ][ _SbF6 ] ₂ ) and dichloro(pentamethylcyclopentadienyl)iridium ( III) One or more of dimers ([Cp*IrCl ₂ ] ₂ ), more preferably pentamethylcyclopentadienyltriacetonitrile-bis(hexafluoroantimonate)rhodium and/or dichloro( Pentamethylcyclopentadienyl)iridium(III) dimer.

When the metal catalyst is dichloro(pentamethylcyclopentadienyl) iridium (III) dimer, the reaction preferably adds bis-trifluoromethanesulfonimide silver salt (AgNTf ₂ ), bis-trifluoromethanesulfonyl Silver imine salt as a chloride ion-snatching agent, used with dichloro(pentamethylcyclopentadienyl)iridium(III) dimer, capable of grabbing dichloro(pentamethylcyclopentadienyl) The chloride ions on the iridium(III) dimer are synthesized, thereby generating in situ a more electron-deficient trivalent iridium catalyst species and enhancing its electrophilicity.

In the present invention, R ¹ and R ² are independently selected from hydrogen, alkyl, cycloalkyl, phenyl, substituted phenyl, naphthyl, furanyl, thienyl, indolyl or pyrrolyl, and R ³ is selected from three Isopropylsilyl, dimethyl tert-butylsilyl or cyclohexyl-containing oxysilyl ether.

Further, R ¹ and R ² are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, benzyl, phenethyl, phenylpropyl, phenyl, naphthyl, furyl , thienyl, indolyl or pyrrolyl, R ³ is selected from triisopropylsilyl (-TIPS), dimethyl tert-butylsilyl (-TMS) or cyclohexyl-containing oxysilyl ether.

Further, R ¹ and R ² are independently selected from hydrogen, methyl, ethyl, benzyl, 4-fluoro-benzyl, 2-chlorobenzyl, 2-bromobenzyl or phenethyl, and R ³ is Triisopropylsilyl (-TIPS).

In the present invention, the nitrogen-oxygen bond-containing alkyne derivative represented by formula (I) is selected from

The compound represented by the formula (II) is obtained from a commercially available alcohol through Mitsnobu reaction with N-hydroxyphthalimide and hydrazinolysis with hydrazine hydrate to obtain the corresponding primary amine, which is then condensed with cyclohexanone.

The compound represented by formula (II) is preferably

The compound represented by formula (III) is selected from

Preferably, the oxidant is selected from one or more of silver acetate, silver carbonate, silver trifluorosulfonate, silver nitrate, copper acetate, cuprous halide, copper halide, iron trihalide and iron nitrate, more preferably copper acetate;

The alkali for adjusting the alkaline conditions is selected from one or more of sodium acetate, cesium acetate, potassium acetate, sodium carbonate, lithium carbonate and potassium phosphate, more preferably sodium acetate.

Preferably, the reaction temperature is 60°C to 150°C, more preferably 80°C to 120°C, and further preferably 100°C;

The reaction time is 8h-48h, more preferably 8h-36h.

In the present invention, the inert solvent is selected from toluene, tetrahydrofuran, 1,4-dioxane, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone, Methyl sulfoxide, acetonitrile, 1,2-dichloroethane, ethanol or acetone, more preferably 1,2-dichloroethane.

Preferably, the molar ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1:1 to 1:4;

The amount of the metal catalyst used is 1 mol % to 5 mol % of the amount of the compound represented by formula (II), more preferably 2 mol %.

In the present invention, the amount of the base is (5-50) mol% of the amount of the compound represented by the formula (II), more preferably 15 mol%;

The amount of the oxidizing agent is (10-300) mol% of the amount of the compound represented by the formula (II), more preferably 30 mol%.

The concentration of the compound represented by the formula (II) in the inert solvent is 0.1mol/L～3.0mol/L, preferably 0.2mol/L; the concentration of the compound represented by the formula (III) in the inert solvent is 0.5mol/L～3.0mol /L, preferably 1.0 mol/L.

In the present invention, the preparation method of the alkyne derivative containing nitrogen-oxygen bond preferably includes the following steps: in an atmosphere of air, sequentially adding the compound represented by formula (II) (0.1 mmol), dichloro (pentamethyl) Cyclopentadienyl)iridium(III) dimer (3.2mg), bistrifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), by syringe The 1,2-dichloroethane solution (1.0 mL) of the compound represented by formula (III) (0.3 mmol) was injected into the reactor and placed at 100° C. for 12 h. The reaction was determined by thin-layer chromatography analysis. After suction filtration through diatomaceous earth, use 400-mesh silica gel to make dry powder by rotary evaporation, and then use column chromatography to separate the reaction product, 400-mesh silica gel 5g, and the developing solvent is petroleum ether and the volume ratio of 200:1 to 20:1. Ethyl acetate yields alkyne derivatives containing nitrogen-oxygen bonds.

In view of the fact that nitroxides derived from alkyl alcohols are prone to rearrangement, oxidation, and elimination reactions to obtain by-products such as ketones, carbonyl compounds, and alkenes, there are few reports on the direct oxidative Csp ³ -H bond functionalization reaction promoted by alcoholic hydroxyl groups. The preparation method of the invention not only provides an efficient and highly selective synthesis method of alkyne derivatives containing nitrogen-oxygen bonds, but also provides a new idea for alcohol-derived nitrogen oxide-induced oxidative Csp ³ -H bond functionalization. In addition, the nitrogen-oxygen bond-containing alkyne derivatives of the present invention contain easily convertible nitrogen-oxygen bonds, which can be reduced to obtain high value-added primary amines and alkynyl-containing polysubstituted alcohol compounds, which can be quickly obtained by one chemical conversion. Two kinds of fine chemicals with high added value, therefore, the present invention will also provide certain theoretical guidance for the field of functionalization reaction of position-selective alkyl Csp ³ -H bond.

For common nitrogen-oxygen bond-containing alkyl compounds, they often contain a large number and variety of Csp ³ -H bonds (primary, secondary, tertiary Csp ³ -H bonds, etc., and even aryl Csp ² -H bonds) ), the catalytic system of the present invention can effectively recognize different kinds of CH bonds, and the reaction generates five-membered organometallic cyclic intermediates in situ through the metal catalyst and the nitrogen atom of the substrate, and the position-specificity is in the first-order Csp ³ -H The alkynylation reaction occurs on the bond to obtain the corresponding alkyne derivative containing nitrogen-oxygen bond, which can realize the position-specific alkynylation of Csp ³ -H bond, and has important synthetic value.

The present invention also provides the application of the nitrogen-oxygen bond-containing alkyne derivative described in the above technical solution and/or the nitrogen-oxygen bond-containing alkyne derivative prepared by the preparation method described in the above technical solution in the preparation of medicines.

The nitrogen-oxygen bond-containing alkyne derivatives of the invention contain easily convertible nitrogen-oxygen bonds, can obtain high value-added primary amines and alkynyl-containing polysubstituted alcohol compounds through reduction, and have good application in the field of organic synthesis prospect. In addition, when R ³ is a substituted silicon group, the alkyne derivatives containing nitrogen-oxygen bonds of the present invention contain a silicon group that is directly connected to the carbon-carbon triple bond of the alkyne and can be easily left, and further terminal alkyne compounds can be obtained.

In the present invention, the alkyne derivatives containing nitrogen-oxygen bonds can be easily converted into alcohol compounds containing alkynyl groups, such as through LAH (lithium aluminum hydride) reduction and TBAF (tetrabutylammonium fluoride) desiliconization, which can be quantitatively to obtain the alkynyl-containing alcohol target product.

In summary, the present invention provides a nitrogen-oxygen bond-containing alkyne derivative, the structural formula of the nitrogen-oxygen bond-containing alkyne derivative is shown in formula (I), wherein R ¹ and R ² are independent is selected from hydrogen, C1-C20 hydrocarbon group, C5-C30 aryl group, C5-C30 substituted aryl group or C5-C30 aromatic heterocyclic group, and R ³ is a substituted silicon group. In the present invention, the nitrogen-oxygen bond-containing alkyne derivatives of the present invention contain easily convertible nitrogen-oxygen bonds, and can be reduced to obtain high value-added primary amines and alkynyl-containing polysubstituted alcohol compounds, which are useful in the field of organic synthesis. Has a good application prospect. In addition, the alkyne derivative containing nitrogen-oxygen bond of the present invention contains a silicon group which is directly connected with the alkyne and can be easily left, and can further obtain a terminal alkyne compound.

Description of drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are required in the description of the embodiments or the prior art.

Fig. 1 is the nuclear magnetic resonance ¹ H spectrum of cyclohexanone O-(5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1a) provided in Example 1 of the present invention;

Fig. ² is the nuclear magnetic resonance13C spectrum of cyclohexanone O-(5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1a) provided in Example 1 of the present invention;

Fig. 3 is the nuclear magnetic resonance of cyclohexanone O-(2-methyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1b) provided in Example 2 of the present invention ¹ H spectrum;

Fig. 4 is the nuclear magnetic resonance of cyclohexanone O-(2-methyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1b) provided in Example 2 of the present invention ¹³ C spectrum;

Fig. 5 is the nuclear magnetic resonance ¹ H spectrum of cyclohexanone O-(6-(triisopropylsilyl)-5-hexynyl-3-yl)oxime ether (1c) provided in Example 3 of the present invention;

Fig. 6 is the nuclear magnetic resonance13C spectrum of cyclohexanone O-(6-(triisopropylsilyl)-5-hexynyl- ³ -yl)oxime ether (1c) provided in Example 3 of the present invention;

Fig. 7 is the nuclear magnetic resonance of cyclohexanone O-(1-phenyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1d) provided in Example 4 of the present invention ¹ H spectrum;

Fig. 8 is the nuclear magnetic resonance of cyclohexanone O-(1-phenyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1d) provided in Example 4 of the present invention ¹³ C spectrum;

Fig. 9 is cyclohexanone O-(1-(4-fluorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1e) provided in Example 5 of the present invention ) of the nuclear magnetic resonance ¹ H spectrum;

Figure 10 is the cyclohexanone O-(1-(4-fluorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1e) provided in Example 5 of the present invention ) of the nuclear magnetic resonance ¹³ C spectrum;

Figure 11 is the cyclohexanone O-(1-(2-chlorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1f) provided in Example 6 of the present invention ) of the nuclear magnetic resonance ¹ H spectrum;

Figure 12 is the cyclohexanone O-(1-(2-chlorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1f) provided in Example 6 of the present invention ) of the nuclear magnetic resonance ¹³ C spectrum;

Figure 13 is the cyclohexanone O-(1-(2-bromophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1 g ) of the nuclear magnetic resonance ¹ H spectrum;

Figure 14 is the cyclohexanone O-(1-(2-bromophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1 g ) of the nuclear magnetic resonance ¹³ C spectrum;

Figure 15 is the nuclear magnetic resonance ¹ of cyclohexanone O-(1-phenyl-6-(triisopropylsilyl)-5-hexyn-3-yl)oxime ether (1h) provided in Example 8 of the present invention H spectrum;

Figure 16 is the nuclear magnetic resonance ¹³ of cyclohexanone O-(1-phenyl-6-(triisopropylsilyl)-5-hexyn-3-yl)oxime ether (1h) provided in Example 8 of the present invention C spectrum;

Figure 17 is the nuclear magnetic resonance ¹ H spectrum of 4-pentyn-2-ol (4a) provided in Example 9 of the present invention;

18 is the nuclear magnetic resonance ¹³ C spectrum of 4-pentyn-2-ol (4a) provided in Example 9 of the present invention.

Detailed ways

The invention provides a nitrogen-oxygen bond-containing alkyne derivative, a preparation method and application thereof, which are used to provide a new nitrogen-oxygen bond-containing alkyne derivative, and broaden the alkyne derivatives containing nitrogen-oxygen bond. type.

The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

In order to further understand the present invention, the present invention will be described in detail below with reference to specific embodiments.

Example 1

In this example, the preparation of cyclohexanone O-(5-(triisopropylsilyl)-4-pentynyl-2-yl) oxime ether (1a) is carried out, and its reaction formula is as follows:

In an atmosphere of air, the nitrogen-oxygen bond-containing compound 2a (15.5 mg, 0.1 mmol) and dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (3.2 mg) were sequentially added to the reactor. , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3a (54.0mg, 0.3mmol) in acetone (1.0 mL) was placed in the reactor at 120°C for 24h, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then column chromatography was used. The reaction product was separated, 5 g of 400-mesh silica gel, and the developing solvent was petroleum ether and ethyl acetate with a volume ratio of 200:1 to 20:1 to obtain cyclohexanone O-(5-(triisopropylsilyl)-4- Pentynyl-2-yl)oxime ether (1a), 25.1 mg, 95% pure, 75% yield.

NMR detection of cyclohexanone O-(5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1a), please refer to Figure 1 to Figure 2, the results are: ¹ H NMR (400MHz, CDCl3): δ4.27-4.23 (m, 1H), 2.64 (dd, J=4.0Hz, 16.8Hz, 1H), 2.46-2.40 (m, 3H), 2.18 (t, J=6.0 Hz, 2H), 1.66-1.65 (m, 2H), 1.59-1.58 (m, 4H), 1.34 (d, J=6.4Hz, 3H), 1.07-1.05 (m, 21H); ¹³ C NMR (100MHz, CDCl3): δ160.3, 105.4, 81.8, 76.4, 32.3, 27.1, 26.8, 25.9, 25.8, 25.4, 18.6, 18.5, 11.3.

This example shows that the compound containing nitrogen-oxygen bond can realize the alkynylation reaction of Csp ³ -H bond at β position of oxygen atom with the assistance of nitrogen-oxygen bond, and the reaction of this example has excellent site selectivity.

Example 2

In this example, the preparation of cyclohexanone O-(2-methyl-5-(triisopropylsilyl)-4-pentynyl-2-yl) oxime ether (1b) is carried out, and its reaction formula is as follows :

Under air atmosphere, the nitrogen-oxygen bond-containing compound 2b (16.9 mg, 0.1 mmol) and dichloro(pentamethylcyclopentadienyl) iridium (III) dimer (3.2 mg) were sequentially added to the reactor. , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3a (54.0mg, 0.3mmol) in acetone (1.0 mL) was placed in the reactor at 120°C for 24h, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then column chromatography was used. The reaction product was separated, 5g of 400-mesh silica gel, and the developing solvent was petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone-O-(2-methyl-5-(triisopropyl) Silyl)-4-pentynyl-2-yl)oxime ether (1b), 27.2 mg, 95% pure, 78% yield.

NMR of cyclohexanone-O-(2-methyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1b), see Figures 3 to 3 4. The results are: ¹ H NMR (400MHz, CDCl ₃ ): δ=2.57(s, 2H), 2.49-2.40(m, 2H), 2.18(t, J=6.0Hz, 2H), 1.70-1.60(m , 2H), 1.58-1.56 (m, 4H), 1.37 (s, 6H), 1.08-1.07 (m, 21H); ¹³ C NMR (100 MHz, CDCl ₃ ): δ=158.2, 105.4, 80.4, 77.5, 31.4 , 30.7, 26.1, 25.0, 24.8, 24.2, 17.6, 10.3.

This example shows that the compound containing nitrogen-oxygen bond can realize the alkynylation reaction of Csp ³ -H bond at β position of oxygen atom with the assistance of nitrogen-oxygen bond, and the reaction of this example has excellent site selectivity.

Example 3

In this example, the preparation of cyclohexanone O-(6-(triisopropylsilyl)-5-hexynyl-3-yl) oxime ether (1c) is carried out, and its reaction formula is as follows:

Under the air atmosphere, the nitrogen-oxygen bond-containing compound 2c (16.9 mg, 0.1 mmol), and the dichloro(pentamethylcyclopentadienyl) iridium (III) dimer (3.2 mg) were successively added to the reactor. , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3b (78mg, 0.3mmol) in acetone (1.0mL) was injected with a syringe ) was placed in the reactor at 120 ° C for 24 hours, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then separated by column chromatography. The reaction product, 5g of 400-mesh silica gel, the developing solvent is petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone O-(6-(triisopropylsilyl)-5-hexane Alkynyl-3-yl)oxime ether (1c), 24.8 mg, 95% pure, 71% yield.

NMR detection of cyclohexanone O-(6-(triisopropylsilyl)-5-hexynyl-3-yl)oxime ether (1c), please refer to Figure 5 to Figure 6, the results are: ¹ H NMR (400MHz, _CDCl3 ): δ=4.08-4.02 (m, 1H), 2.61 (dd, J=4.4Hz, 16.8Hz, 1H), 2.51-2.43 (m, 3H), 2.18 (m, 2H) , 1.73-1.64 (m, 2H), 1.59-1.58 (m, 6H), 1.11-1.04 (m, 21H), 0.95 (t, J=7.2Hz, 3H); ¹³ C NMR (100MHz, CDCl ₃ ): δ=160.4, 105.5, 81.7, 81.3, 32.3, 27.1, 25.9, 25.8, 25.43, 25.41, 24.6, 18.6, 18.5, 17.7, 11.3, 9.7.

This example shows that compounds containing nitrogen-oxygen bonds can realize the alkynylation reaction of β-position Csp ³ -H bonds of oxygen atoms with the assistance of nitrogen-oxygen bonds, even if the compounds containing nitrogen-oxygen bonds also have γ-position primary Csp ³ -H bond.

Example 4

In this example, the preparation of cyclohexanone O-(1-phenyl-5-(triisopropylsilyl)-4-pentynyl-2-yl) oxime ether (1d) is carried out, and its reaction formula is as follows :

Under the air atmosphere, the nitrogen-oxygen bond-containing compound 2d (23.1 mg, 0.1 mmol), dichloro (pentamethylcyclopentadienyl) iridium (III) dimer (3.2 mg) were sequentially added to the reactor , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3b (78mg, 0.3mmol) in acetone (1.0mL) was injected with a syringe ) was placed in the reactor at 120°C for 18h, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, which was then separated by column chromatography. The reaction product, 5g of 400-mesh silica gel, and the developing solvent are petroleum ether and ethyl acetate with a volume ratio of 200:1 to 20:1 to obtain cyclohexanone O-(1-phenyl-5-(triisopropylsilyl) )-4-pentynyl-2-yl)oxime ether (1d), 32.9 mg, 95% pure, 80% yield.

NMR detection of cyclohexanone O-(1-phenyl-5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1d), see Figures 7 to 8 , the results are: ¹ H NMR (400MHz, CDCl ₃ ): δ7.27-7.26 (m, 4H), 7.23-7.18 (m, 1H), 4.37-4.31 (m, 1H), 3.11 (dd, J=5.6 Hz,8.8Hz,1H),3.02(dd,J=6.8Hz,14.0Hz,1H),2.58-2.49(m,2H),2.47-2.43(m,2H),2.19-2.16(m,2H), 1.65-1.56 (m, 6H), 1.25 (s, 2H), 1.10-1.09 (m, 19H); ¹³ C NMR (100 MHz, CDCl ₃ ): δ=160.6, 138.4, 129.7, 128.1, 126.1, 105.3, 82.5 , 80.8, 38.4, 32.2, 29.7, 27.1, 25.8, 24.2, 18.7, 18.6, 18.5, 18.4, 17.7, 12.3, 11.4, 11.2.

This example shows that compounds containing nitrogen-oxygen bonds can achieve regioselective β-Csp ³ -H alkynylation of oxygen atoms with the assistance of nitrogen-oxygen bonds, and the reaction does not occur in the common more active benzyl position or aryl CH bond position is converted.

Example 5

In this example, the preparation of cyclohexanone O-(1-(4-fluorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1e), the reaction The formula is as follows:

Under the air atmosphere, the nitrogen-oxygen bond-containing compound 2e (24.9 mg, 0.1 mmol), dichloro(pentamethylcyclopentadienyl) iridium (III) dimer (3.2 mg) were sequentially added to the reactor , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3a (54.0mg, 0.3mmol) in acetone (1.0 mL) in the reactor and placed at 120°C for 20h. The reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth and concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then column chromatography was used. The reaction product was separated, 5 g of 400-mesh silica gel, and the developing solvent was petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone O-(1-(4-fluorophenyl)-5-( Triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1e), 31.3 mg, 95% pure, 73% yield.

NMR of cyclohexanone O-(1-(4-fluorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1e), see figure 9 to Figure 10, the results are: ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.33-7.31 (m, 2H), 7.16-7.13 (m, 2H), 4.45-4.41 (m, 2H), 3.26 (dd , J＝4.8Hz, 14.0Hz, 1H), 3.11(dd, J＝8.0Hz, 14.0Hz, 1H), 2.62(d, J＝5.2Hz, 2H), 2.49-2.35(m, 2H), 2.13( d, J=6.0Hz, 2H), 1.63-1.54 (m, 6H), 1.09-1.08 (m, 21H); ¹³ C NMR (100 MHz, CDCl ₃ ): δ=159.6, 135.5, 133.5, 130.9, 128.3, 126.6, 125.3, 104.0, 81.5, 78.1, 35.5, 31.1, 26.0, 24.8, 24.7, 24.5, 24.0, 17.6, 17.54, 17.48, 16.7, 11.3, 10.3.

This example shows that compounds containing nitrogen-oxygen bonds can realize the regioselective β-position Csp ³ -H bond alkynylation of oxygen atoms with the assistance of nitrogen-oxygen bonds, and the reaction is compatible with common reactions in the fields of materials and medicine. Fluorine functional group.

Example 6

In this example, the preparation of cyclohexanone O-(1-(2-chlorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1f), the reaction The formula is as follows:

Under the air atmosphere, the nitrogen-oxygen bond-containing compound 2f (26.5mg, 0.1mmol), dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (3.2mg) were added to the reactor in turn , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3c (85.6mg, 0.2mmol) in acetone (1.0 mL) in the reactor and placed at 120°C for 16h, and the TLC analysis confirmed the end of the reaction. The reaction solution was filtered through diatomaceous earth and concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then column chromatography was used. The reaction product was separated, 5g of 400-mesh silica gel, and the developing solvent was petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone O-(1-(2-chlorophenyl)-5-( Triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1f), 33.8 mg, 95% pure, 76% yield.

NMR of cyclohexanone O-(1-(2-chlorophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1f), see figure 11 to Figure 12, the results are: ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.21 (dd, J=5.6 Hz, 8.4 Hz, 1H), 6.95 (t, J=8.8 Hz, 2H), 4.33-4.27 (m,1H),3.09(dd,J＝5.6Hz,9.6Hz,1H),2.98(dd,J＝6.8Hz,14.0Hz,1H),2.56(dd,J＝4.0Hz,16.8Hz,1H) , 2.45(dd, J=7.2Hz, 16.8Hz, 3H), 2.19-2.16(m, 2H), 1.60-1.57(m, 6H), 1.10-1.07(m, 21H); ¹³ C NMR (100MHz, CDCl) ₃ ): δ=160.8, 134.0, 133.9, 131.1, 115.0, 114.8, 105.1, 82.6, 80.7, 37.5, 32.2, 29.7, 27.1, 25.83, 25.78, 25.6, 24.2, 18.7, 18.5, 17.8, 17.7, 12.3, .

This example shows that compounds containing nitrogen-oxygen bonds can achieve regioselective β-Csp ³ -H alkynylation of oxygen atoms with the assistance of nitrogen-oxygen bonds, and there is no alkynylation at benzylic or aryl chlorides. The reaction occurs at the site, showing good site selectivity and chemical selectivity.

Example 7

In this example, the preparation of cyclohexanone O-(1-(2-bromophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl) oxime ether (1g), the reaction The formula is as follows:

In an atmosphere of air, the nitrogen-oxygen bond-containing compound 2g (30.9mg, 0.1mmol), dichloro(pentamethylcyclopentadienyl)iridium(III) dimer (3.2mg) were sequentially added to the reactor , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3a (54.0mg, 0.3mmol) in acetone (1.0 mL) was placed in the reactor at 120°C for 24h, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then column chromatography was used. The reaction product was separated, 5g of 400-mesh silica gel, and the developing solvent was petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone O-(1-(2-bromophenyl)-5-( Triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1 g), 31.8 mg, 95% pure, 65% yield.

NMR of cyclohexanone O-(1-(2-bromophenyl)-5-(triisopropylsilyl)-4-pentyn-2-yl)oxime ether (1g), see figure 13 to Figure 14, the results are: ¹ H NMR (400 MHz, CDCl ₃ ): δ=7.52 (d, J=8.4 Hz, 1H), 7.33 (d, J=7.6 Hz, 1H), 7.20 (t, J= 7.2Hz, 1H), 7.07-7.03(m, 1H), 4.47-4.47(m, 1H), 3.29-3.09(m, 2H), 2.65-2.63(m, 1H), 2.44-2.39(m, 2H) , 2.19-2.13 (m, 3H), 163-1.54 (m, 6H), 1.26-1.25 (m, 3H), 1.13-1.02 (m, 21H); ¹³ C NMR (100MHz, CDCl ₃ ): δ=159.6 ,158.8,137.6,137.3,131.6,130.9,130.8,126.6,126.0,124.0,104.0,81.5,78.1,40.7,38.0,31.2,31.1,26.05,26.02,24.9,24.8,24.7.,24.5,24 .

This example shows that compounds containing nitrogen-oxygen bonds can realize the regioselective β-Csp ³ -H bond alkynylation of oxygen atoms with the assistance of nitrogen-oxygen bonds, and the reaction has excellent regioselectivity. More importantly, the reaction is compatible with aryl bromide compounds widely used in coupling reactions.

Example 8

The present embodiment carries out the preparation of cyclohexanone O-(1-phenyl-6-(triisopropylsilyl)-5-hexyn-3-yl) oxime ether (1h), and its reaction formula is as follows:

Under the air atmosphere, the nitrogen-oxygen bond-containing compound 2h (24.5 mg, 0.1 mmol), dichloro(pentamethylcyclopentadienyl) iridium (III) dimer (3.2 mg) were sequentially added to the reactor , bis-trifluoromethanesulfonimide silver salt (5.8mg), lithium carbonate (14.8mg) and silver acetate (33.4mg), a solution containing alkyne compound 3a (78mg, 0.3mmol) in acetone (1.0mL) was injected with a syringe ) was placed in the reactor at 120 ° C for 24 hours, and the reaction was determined by thin-layer chromatography analysis. The reaction solution was filtered through diatomaceous earth, and then concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then separated by column chromatography. The reaction product, 5g of 400-mesh silica gel, and the developing solvent are petroleum ether and ethyl acetate with a volume ratio of 100:1 to 20:1 to obtain cyclohexanone O-(1-phenyl-6-(triisopropylsilyl) )-5-hexyn-3-yl)oxime ether (1 h), 33.1 mg, 95% pure, 78% yield.

NMR detection of cyclohexanone O-(1-phenyl-6-(triisopropylsilyl)-5-hexyn-3-yl)oxime ether (1h), see Figure 15 to Figure 16, The results were: ¹ H NMR (400 MHz, CDCl ₃ ): δ=7.19-7.17 (m, 2H), 7.13-7.07 (m, 3H), 4.13-4.01 (m, 1H), 2.71-2.39 (m, 3H) ,2.47-2.39(m,3H),2.13-2.10(m,2H),1.59-1.52(m,6H), ^1.18-1.17 (m,2H),1.04-0.94(m,21H); 100MHz, CDCl ₃ ): δ=160.6, 142.3, 128.45, 128.42, 128.3, 125.7, 105.3, 80.0, 79.4, 37.5, 34.3, 32.35, 32.28, 31.8, 31.7, 25.9, 25.45, 25.40, 18.6, 11.3.

This example shows that compounds containing nitrogen-oxygen bonds can realize the alkynylation reaction of the β-position Csp ³ -H bond of the oxygen atom with the assistance of nitrogen-oxygen bonds. When the more active benzylic or aryl CH bond is reacted, and the secondary Csp ² -H bond at β position exists in the substrate at the same time, the reaction only occurs on the primary Csp ³ -H bond.

Example 9

The present embodiment carries out the preparation of 4-pentyn-2-ol (4a), and its reaction formula is as follows:

Under nitrogen atmosphere, a solution of cyclohexanone O-(5-(triisopropylsilyl)-4-pentynyl-2-yl)oxime ether (1a) (67.0 mg, 0.2 mmol) in ether ( 4.0 mL) was charged with lithium aluminum hydride (LAH, 19 mg, 0.5 mmol), and the reaction was carried out at room temperature for 48 hours. After the reaction solution was suction filtered through celite, tetrabutylammonium fluoride (104.4 mg, 0.4 mmol) was added, and the reaction was continued at room temperature for 1 hour. The reaction solution was filtered through diatomaceous earth and concentrated by rotary evaporation with 400-mesh silica gel to make dry powder, and then the reaction product was separated by column chromatography, 5 g of 400-mesh silica gel, and the developing solvent was a volume ratio of 100:1 to 20:1 Petroleum ether and ethyl acetate were used to obtain alkynyl-containing alcohol derivative 4-pentyn-2-ol (4a), 14.4 mg, with a purity of 95% and a yield of 86%.

NMR detection of 4-pentyn-2-ol (4a), please refer to Figure 17 to Figure 18, the results are: ¹ H NMR (400MHz, CDCl ₃ ): δ=3.92-3.91 (m, 1H), 2.68 -2.48 (m, 1H), 2.36-2.25 (m, 2H), 2.03-2.02 (m, 1H), 1.23-1.21 (m, 3H); ¹³ C NMR (100 MHz, CDCl ₃ ): δ=80.9, 66.1 , 28.7, 22.1.

This example shows that the alkyne derivatives containing nitrogen-oxygen bonds of the present invention can be reduced and desiliconized to obtain alcohol derivatives containing terminal alkynes, thereby realizing the formal alcohol-induced Csp ³ -H bond alkynyl group chemical reaction.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (3)

1. A method for preparing an alkyne derivative containing a nitrogen-oxygen bond is characterized by comprising the following steps:

reacting a compound shown in a formula (II) with a compound shown in a formula (III) in the presence of a catalyst to obtain an alkyne derivative containing a nitrogen-oxygen bond shown in the formula (I);

wherein,

R¹and R²Independently selected from hydrogen, alkyl of C1-C20, aryl of C5-C30, substituted aryl of C5-C30 or aromatic heterocyclic radical of C5-C30, R³For replacing silicon base, X is hydrogen, bromine, chlorine, iodine or an iodine-containing heterocyclic group;

the catalyst is a metal catalyst, and the metal of the metal catalyst is selected from iridium;

the metal catalyst is selected from dichloro (pentamethylcyclopentadienyl) iridium (III) dimer;

the reaction of the compound shown in the formula (II) and the compound shown in the formula (III) in the presence of a catalyst is specifically as follows:

dissolving a compound shown as a formula (II) and a compound shown as a formula (III) in an inert solvent, and reacting under the action of an oxidant, bis (trifluoromethanesulfonyl) imide silver salt and a metal catalyst under an alkaline condition;

the oxidant is selected from silver acetate;

the base to adjust the alkaline conditions is selected from lithium carbonate.

2. The method for preparing the compound of claim 1, wherein the reaction temperature is 60 ℃ to 150 ℃;

the reaction time is 8-48 h.

3. The preparation method according to claim 1, wherein the molar ratio of the compound represented by the formula (II) to the compound represented by the formula (III) is 1:1 to 1: 4;

the dosage of the metal catalyst is 1-5 mol% of the dosage of the compound shown in the formula (II).

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