CN111187287B - Method for catalyzing hydroboration and hydrosilation reaction of nitrogen heterocyclic compound - Google Patents
Method for catalyzing hydroboration and hydrosilation reaction of nitrogen heterocyclic compound Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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Abstract
The invention relates to a method for catalyzing hydroboration and hydrosilation reactions of nitrogen heterocyclic compounds. The invention discloses a metal zinc complex shown in a formula (1) or a formula (2), and discloses an application of the metal zinc complex shown in the formula (1) or the formula (2) in hydroboration or hydrosilation of a catalytic nitrogen heterocyclic compound. The invention provides a method for selectively generating 1, 2-addition hydroboration or hydrosilation products by catalyzing nitrogen heterocyclic compounds, which has the advantages of simple operation, mild reaction conditions and wide substrate applicability.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a method for catalyzing hydroboration and hydrosilation reactions of nitrogen heterocyclic compounds.
Background
The dihydroquinoline derivatives are not only important organic synthesis intermediates, but also widely applied to drug synthesis because of having biological pharmacological activities such as anti-inflammatory and anti-tumor activities. Due to their numerous biopharmacological activities, the synthesis of such compounds has become a research hotspot in this field.
Generally, the following two methods are available for preparing dihydroquinolines: (1) using alkali metal or metal hydride catalysis; (2) and (4) directly hydrogenating. However, the conventional preparation methods have problems such as excessive reduction, severe reaction conditions, narrow substrate range and difficulty in separating 1, 2-and 1, 4-addition products.
Therefore, the synthesis of the high-efficiency metal catalyst for catalyzing the hydroboration and hydrosilation reactions of the quinoline derivatives has important significance.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for catalyzing hydroboration and hydrosilation reactions of nitrogen heterocyclic compounds, and discloses a metal zinc complex which is used for catalyzing the reaction of the nitrogen heterocyclic compounds and borane or silane to selectively generate 1, 2-addition hydroboration or hydrosilation products, so that the operation is simple, the reaction condition is mild, and the applicability of substrates is wide.
The first purpose of the invention is to disclose a metal zinc complex, the structural formula of which is shown as formula (1) or formula (2):
wherein R is1、R2、R3、R4、R5、R6、R7And R8Are each independently selected from C1-C4Alkyl or halogen.
Further, C1-C4Alkyl is methyl, ethyl, isopropyl or tert-butyl; halogen is chlorine or bromine.
Preferably, in the metal zinc complex represented by the formula (1), R1、R2、R3And R4All are tertiary butyl groups, i.e., having the formula:
preferably, in the metal zinc complex represented by the formula (2), R5、R6、R7And R8Are all tertiary butyl groups, i.e. the structural formula is as follows:
the preparation method and the route of the metal zinc complex shown in the formula (1) or the formula (2) are respectively as follows:
a ligand represented by the formula (3) or (4) and ZnEt2Reacting in an organic solvent at 30 ℃, and standing at 0 ℃ after the reaction is completed until colorless transparent crystals are separated out to respectively obtain the metal zinc complex shown in the formula (1) or the formula (2);
the second purpose of the invention is to disclose the application of the metal zinc complex shown in the formula (1) or the formula (2) in catalyzing hydroboration or hydrosilation reaction of nitrogen heterocyclic compound; wherein the hydroboration reagent for hydroboration reaction is pinacol borane, and the hydrosilation reagent for hydrosilation reaction is phenyl silane.
Further, the nitrogen heterocyclic compound contains 1 to 2 nitrogen heterocycles.
Furthermore, the nitrogen heterocyclic compound contains 4-13 carbon atoms; the nitrogen heterocyclic compound is one or more of quinoline compounds and derivatives thereof, pyrimidine compounds and derivatives thereof, phenanthridine compounds and derivatives thereof, quinazoline compounds and derivatives thereof, and benzimidazole compounds.
Further, the nitrogen heterocyclic compound is quinoline, methylquinoline, methoxyquinoline, halogenated quinoline, acridine, isoquinoline, methylisoquinoline, pyrimidine, pyrazine, phenanthridine, quinazoline or N-methylbenzimidazole.
Further, the reaction temperature of the hydroboration or hydrosilation reaction is 30 to 80 deg.C (preferably 30 to 40 deg.C), and the reaction is carried out in a deuterated reagent.
Furthermore, the molar ratio of the nitrogen heterocyclic compound, the pinacol borane or the phenylsilane and the metal zinc complex is 10-20:10-20: 1.
In the invention, the structures of pinacolborane (HBpin) and phenylsilane are as follows in sequence:
further, when the nitrogen heterocyclic compound is quinoline, methylquinoline, methoxyquinoline, halogenated quinoline, acridine, isoquinoline, methylisoquinoline, phenanthridine, quinazoline or N-methylbenzimidazole, the nitrogen heterocyclic compound reacts with pinacol borane to generate a primary addition product containing an N-B covalent bond.
Further, when the nitrogen heterocyclic compound is pyrimidine, pyrazine or quinazoline, the nitrogen heterocyclic compound reacts with pinacol borane to generate a secondary addition product containing an N-B covalent bond.
Further, when the nitrogen heterocyclic compound is quinoline, methylquinoline, methoxyquinoline, halogenated quinoline, acridine, isoquinoline or N-methylbenzimidazole, the nitrogen heterocyclic compound reacts with the phenylsilane to generate a primary addition product or a secondary addition product containing an N-Si covalent bond.
Further, the reaction time of hydroboration or hydrosilation is 1-48 h.
Further, the hydroboration or hydrosilation reaction is carried out under the closed condition and the anhydrous condition with the protective atmosphere.
Further, the protective atmosphere is an argon atmosphere or a nitrogen atmosphere.
Further, the deuterated reagent is deuterated benzene (C)6D6) Or deuterated chlorobenzene (C)6ClD5)。
The third purpose of the invention is to disclose a method for catalyzing hydroboration reaction of nitrogen heterocyclic compound, which comprises the following steps:
under the action of a protective atmosphere, reacting an nitrogen heterocyclic compound with pinacol borane in a deuteroreagent at 30-80 ℃ (preferably at 30-40 ℃) under the catalytic action of a metal zinc complex shown in the formula (1); the mol ratio of the nitrogen heterocyclic compound to the pinacol borane to the metal zinc complex is 10-20:10-20: 1.
The fourth purpose of the invention is to disclose a method for catalyzing hydrosilation reaction of nitrogen heterocyclic compound, which comprises the following steps:
under the action of a protective atmosphere, reacting an nitrogen heterocyclic compound with phenylsilane in a deuterated reagent at 30-80 ℃ (preferably at 30-40 ℃) under the catalytic action of a metal zinc complex shown in the formula (1); the mol ratio of the nitrogen heterocyclic compound to the phenylsilane to the metal zinc complex is 10-20:10-20: 1.
In the present invention, taking quinoline as an example of a reaction substrate, the reaction principle of the hydroboration reaction of the nitrogen heterocyclic compound catalyzed by the metal zinc complex (abbreviated as [ Zn ] -Et) shown in formula (1) is as follows: firstly, reacting a metal zinc complex with HBpin to obtain A, coordinating quinoline and A to form B, and then carrying out addition reaction on a C ═ N bond of quinoline and a Zn-H bond of A to form a dihydroquinoline zinc intermediate C. Then the double decomposition reaction is carried out between the C and a molecule of HBpin, and a target product and A are obtained through a transition state D, so that the catalytic cycle is completed. The specific principle route is as follows:
when the hydrogenation agent is phenylsilane, the reaction mechanism is the same as above.
In the present invention, the reaction principle of the metal zinc complex (abbreviated as [ Zn ] -Et) represented by formula (1) for catalyzing the hydrosilation reaction of the nitrogen heterocyclic compound is as follows, taking the reaction substrate as quinoline for example: and (3) reacting [ Zn ] -Et with phenylsilane to generate a Zn-H compound, adding a C ═ N bond and a Zn-H bond of quinoline, carrying out double decomposition reaction with one molecule of phenylsilane to obtain an addition product, and regenerating the Zn-H compound. Unlike borane reactions, the reaction of quinoline with silane undergoes two additions to yield a twice-added product.
The mechanism of the metal zinc complex shown in the formula (2) for catalyzing hydroboration or hydrosilation reaction of the nitrogen heterocyclic compound is similar to that of the metal zinc complex shown in the formula (1).
By the scheme, the invention at least has the following advantages:
the preparation method of the metal zinc complex is simple, and the reaction operation is simple and convenient.
The invention also discloses the application of the metal zinc complex in catalyzing hydroboration or hydrosilation reaction of the nitrogen heterocyclic compound, and the catalyst is adopted to ensure that the reaction condition of hydroboration or hydrosilation reaction of the nitrogen heterocyclic compound is mild, and the 1, 2-addition product can be selectively generated, so that the yield is high, and the application range of the substrate is wide.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a metal zinc complex used in the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a metal zinc complex used in the present invention;
FIG. 3 is nuclear magnetic hydrogen spectrum of hydroboration product synthesized in example 1 of the present invention;
FIG. 4 is nuclear magnetic hydrogen spectrum of hydroboration product synthesized in example 2 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 3 of the present invention;
FIG. 6 is nuclear magnetic hydrogen spectrum of hydroboration product synthesized in example 4 of the present invention;
FIG. 7 is nuclear magnetic hydrogen spectrum of hydroboration product synthesized in example 5 of the present invention;
FIG. 8 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 6 of the present invention;
FIG. 9 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 7 of the present invention;
FIG. 10 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 8 of the present invention;
FIG. 11 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 9 of the present invention;
FIG. 12 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 10 of the present invention;
FIG. 13 is a nuclear magnetic hydrogen spectrum of a hydroborated product synthesized in example 11 of the present invention;
FIG. 14 is nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 12 of the present invention;
FIG. 15 is a nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 13 of the present invention;
FIG. 16 is a nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 14 of the present invention;
FIG. 17 is a nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 15 of the present invention;
FIG. 18 is a nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 16 of the present invention;
FIG. 19 is a nuclear magnetic hydrogen spectrum of a hydrosilation product synthesized in example 17 of the present invention.
FIG. 20 is a nuclear magnetic hydrogen spectrum of a hydroboration product synthesized in example 18 of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, the catalyst metal zinc complexes used in examples 1 to 17 of the present invention were prepared as follows:
the ligand (1.57g, 3mmol) was weighed in a reaction flask according to the above reaction scheme, 20mL hexane was added, after dissolution by stirring, ZnEt was added2The reaction mixture was concentrated to 5mL under stirring at 30 ℃ overnight, and after standing at 0 ℃ for a while, colorless transparent crystals (1.67g, 90%) were precipitated. The nuclear magnetic hydrogen spectrum of the product is shown in figure 1.
In example 18 of the present invention, a method for preparing a metal zinc complex as a catalyst used was as follows:
weighing ligand (3mmol) in a reaction flask according to the raw materials in the reaction route, adding 20mL of hexane, stirring to dissolve, adding ZnEt2The reaction mixture was concentrated to 5mL, and the mixture was left at 0 ℃ for several days to precipitate colorless transparent crystals (1.61g, 85%). The nuclear magnetic hydrogen spectrum of the product is shown in FIG. 2.
Example 1
The embodiment provides a method for catalyzing a hydroboration reaction of quinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 35.5. mu.L (0.3mmol) of quinoline are added, the tube is sealed, and the reaction is carried out for 12h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 92% using it as an internal standard, wherein the ratio of 1, 2-to 1, 4-addition product was 22: 1.
The target product has the following structural formula:
example 2
The embodiment provides a method for catalyzing hydroboration reaction of 3-methylquinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6In the method, 29 mu L (0.2mmol) of pinacolborane and 40.0 mu L (0.3mmol) of 3-methylquinoline are added into the solution, a tube is sealed, and the reaction is carried out for 1h at the temperature of 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 92% using this as an internal standard. The target product has the following structural formula:
example 3
The embodiment provides a method for catalyzing hydroboration reaction of 3-chloroquinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 38.6. mu.L (0.3mmol) of 3-chloroquinoline are added, the tube is sealed, and the reaction is carried out for 2h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 90% using this as an internal standard. The target product has the following structural formula:
example 4
The embodiment provides a method for catalyzing hydroboration reaction of 4-methoxyquinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 42.6. mu.L (0.3mmol) of 4-methoxyquinoline are added, the tube is sealed, and the reaction is carried out for 1.5h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 97% using this as an internal standard. The target product has the following structural formula:
example 5
The embodiment provides a method for catalyzing a hydroboration reaction of isoquinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 35.3. mu.L (0.3mmol) of isoquinoline were added, the tube was sealed, and the reaction was carried out at 30 ℃ for 1.5h under the conditions of no water and no oxygen and under the protection of argon. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 97% using this as an internal standard. The target product has the following structural formula:
example 6
The embodiment provides a method for catalyzing a hydroboration reaction of phenanthridine and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution were added 29. mu.L (0.2mmol) of pinacolborane and 53.8mg (0.3mmol)Phenanthridine, sealing the tube, and reacting for 8 hours at 30 ℃ under the conditions of no water and no oxygen and adopting argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 96% using this as an internal standard. The target product has the following structural formula:
example 7
The embodiment provides a method for catalyzing a hydroboration reaction of acridine and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 53.8mg (0.3mmol) of acridine are added, the tube is sealed, and the reaction is carried out for 4h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 96% using this as an internal standard. The target product has the following structural formula:
example 8
The embodiment provides a method for catalyzing a hydroboration reaction of pyrimidine and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6In the method, 58 mu L (0.4mmol) of pinacolborane and 15.8 mu L (0.2mmol) of pyrimidine are added into the solution, a tube is sealed, and the reaction is carried out for 12h at the temperature of 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 99% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 9
The embodiment provides a method for catalyzing a hydroboration reaction of pyrazine and pinacol borane by using 10 mol% of metal zinc complex at 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6In the method, 58 mu L (0.4mmol) of pinacolborane and 15.6 mu L (0.2mmol) of pyrazine are added into the solution, a tube is sealed, and the reaction is carried out for 12h at the temperature of 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 99% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 10
The embodiment provides a method for catalyzing hydroboration reaction of quinazoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 58 μ L (0.4mmol) of pinacolborane and 26.0mg (0.2mmol) of quinazoline are added, the tube is sealed, and the reaction is carried out for 24 hours at the temperature of 30 ℃ under the conditions of no water and no oxygen and the protection of argon. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 95% using this as an internal standard. The target product has the following structural formula:
example 11
The embodiment provides a method for catalyzing hydroboration reaction of N-methylbenzimidazole and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, and the method comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 39.6mg (0.3mmol) of N-methylbenzimidazole are added, the tube is sealed, and the reaction is carried out for 6h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 94% using this as an internal standard. The target product has the following structural formula:
example 12
The embodiment provides a method for catalyzing the hydrosilation reaction of quinoline and phenylsilane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 47.2. mu.L (0.4mmol) of quinoline were added, the tube was sealed, and the mixture was reacted at 30 ℃ for 24 hours under anhydrous and oxygen-free conditions under an argon atmosphere. After the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 76% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 13
The embodiment provides a method for catalyzing hydrosilylation reaction of 4-methylquinoline and phenylsilane by using 10 mol% of metal zinc complex at 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 53. mu.L (0.4mmol) of 4-methylquinoline are added, the tube is sealed, and the mixture is reacted for 24 hours at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 88% using it as an internal standard. The target product has the following structural formula:
example 14
The embodiment provides a method for catalyzing hydrosilation reaction of 6-chloroquinoline and phenylsilane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 65.4mg (0.4mmol) of 6-chloroquinoline were added, the tube was sealed, and the mixture was reacted at 30 ℃ for 24 hours under anhydrous and oxygen-free conditions under an argon atmosphere. After the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 82% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 15
The embodiment provides a method for catalyzing hydrosilylation of isoquinoline and phenylsilane by using 10 mol% of metal zinc complex at 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 47. mu.L (0.4mmol) of isoquinoline were added, the tube was sealed, and the mixture was reacted at 30 ℃ for 2 hours under anhydrous and oxygen-free conditions under an argon atmosphere. After completion of the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction mixture, and the amount was calculated using the amount as an internal standardThe nuclear magnetic yield of the target product is 95%. The target product has the following structural formula:
example 16
The embodiment provides a method for catalyzing hydrosilation reaction of acridine and phenylsilane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 71.7mg (0.4mmol) of acridine are added, the tube is sealed, and the mixture is reacted for 3d at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 87% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 17
The embodiment provides a method for catalyzing hydrosilation reaction of N-methylbenzimidazole and phenylsilane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, and the method comprises the following specific steps:
12.3mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 25. mu.L (0.2mmol) of phenylsilane and 52.9mg (0.4mmol) of N-methylbenzimidazole were added, the tube was sealed, and the mixture was reacted at 30 ℃ for 24 hours under anhydrous and oxygen-free conditions under an argon atmosphere. After the reaction, 13.7mg (0.05mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 85% using the triphenylmethylsilane as an internal standard. The target product has the following structural formula:
example 18
The embodiment provides a method for catalyzing a hydroboration reaction of quinoline and pinacol borane by using 10 mol% of metal zinc complex at the temperature of 30 ℃, which comprises the following specific steps:
12.6mg (0.02mmol) of the metal zinc complex are dissolved in 0.5mL of C6D6To the solution, 29. mu.L (0.2mmol) of pinacolborane and 35.5. mu.L (0.3mmol) of quinoline are added, the tube is sealed, and the reaction is carried out for 48h at 30 ℃ under the conditions of no water and no oxygen and argon protection. After the reaction, 27.4mg (0.1mmol) of triphenylmethylsilane was added to the reaction solution, and the nuclear magnetic yield of the target product was calculated to be 80% using it as an internal standard, wherein the ratio of 1, 2-to 1, 4-addition product was 9: 1.
The target product has the following structural formula:
the above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A metal zinc complex is characterized in that the structural formula is shown as a formula (1) or a formula (2):
wherein R is1、R2、R3、R4、R5、R6、R7And R8Are each independently selected from C1-C4Alkyl or halogen.
2. The metallic zinc complex of claim 1, wherein: said C is1-C4Alkyl is methyl, ethyl, isopropyl or tert-butyl; the halogen is chlorine or bromine.
3. The metallic zinc complex of claim 1, wherein: r1、R2、R3、R4、R5、R6、R7And R8Are all tert-butyl.
4. Use of a zinc metal complex according to any one of claims 1 to 3 for catalysing hydroboration or hydrosilation of nitrogen heterocycles to produce a 1, 2-addition product containing an N-Si covalent bond or an N-B covalent bond; wherein the hydroboration reagent for hydroboration reaction is pinacol borane
The hydrosilation reagent for hydrosilation is phenylsilane
。
5. Use according to claim 4, characterized in that: the nitrogen heterocyclic compound contains 1-2 nitrogen heterocycles.
6. Use according to claim 4, characterized in that: the nitrogen heterocyclic compound contains 4-13 carbon atoms; the nitrogen heterocyclic compound is one or more of a substituted or unsubstituted quinoline compound, a substituted or unsubstituted pyrimidine compound, a substituted or unsubstituted phenanthridine compound, a substituted or unsubstituted quinazoline compound and a substituted or unsubstituted benzimidazole compound.
7. Use according to claim 4, characterized in that: the nitrogen heterocyclic compound is quinoline, methylquinoline, methoxyquinoline, halogenated quinoline, acridine, isoquinoline, methylisoquinoline, pyrimidine, pyrazine, phenanthridine, quinazoline or N-methylbenzimidazole.
8. Use according to claim 4, characterized in that: the reaction temperature of hydroboration or hydrosilation is 30-80 deg.C, and the reaction is carried out in deuterated reagent.
9. A method for catalyzing hydroboration reaction of nitrogen heterocyclic compound is characterized by comprising the following steps:
reacting an azacyclic compound with pinacolborane in a deuterated reagent at 30-80 ℃ under the catalysis of the metal zinc complex of any one of claims 1-3 in a protective atmosphere; the molar ratio of the nitrogen heterocyclic compound to the pinacol borane to the metal zinc complex is 10-20:10-20: 1.
10. A method of catalyzing a hydrosilation reaction of a nitrogen heterocyclic compound, comprising the steps of:
reacting nitrogen heterocyclic compound and phenyl silane in deutero reagent at 30-80 ℃ under the catalysis of metal zinc complex in any one of claims 1-3 under the action of protective atmosphere; the molar ratio of the nitrogen heterocyclic compound to the phenylsilane to the metal zinc complex is 10-20:10-20: 1.
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| CN102060718A (en) * | 2010-11-30 | 2011-05-18 | 华东理工大学 | Polydentate amino monophenoloxy zinc complex compound as well as preparation method and application thereof |
| CN102617369A (en) * | 2012-02-17 | 2012-08-01 | 华东理工大学 | Similar salan monophenol ligand metal complexes as well as preparation method and application thereof |
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| CN102060718A (en) * | 2010-11-30 | 2011-05-18 | 华东理工大学 | Polydentate amino monophenoloxy zinc complex compound as well as preparation method and application thereof |
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