CN118147664A

CN118147664A - Binuclear amino acid-cobalt complex in catalysis of allene C (sp2) Use of selective functionalization of H bonds

Info

Publication number: CN118147664A
Application number: CN202410102443.5A
Authority: CN
Inventors: 张胜; 李漫波; 梁雅婷; 冯佳仪; 金晓丽; 李鑫
Original assignee: Anhui University
Current assignee: Anhui University
Priority date: 2024-01-25
Filing date: 2024-01-25
Publication date: 2024-06-07

Abstract

The invention discloses an application of a mu-OH bridged dinuclear amino acid-cobalt complex in catalyzing selective functionalization of a diene C (sp ²) -H bond. The invention creatively selects the mu-OH bridged dinuclear amino acid-cobalt complex as the catalyst, contains a plurality of alkaline sites, performs electrocatalytic hydrogen evolution reaction on the diene, can solve the problem of high inertia and low selectivity of the diene reaction, has good catalytic performance and good selectivity when the mu-OH bridged dinuclear amino acid-cobalt complex catalyzes hydrogen in C (sp ²) -H on the diene to react; in addition, the mu-OH bridged dinuclear amino acid-cobalt complex is matched with a proper reaction solvent, so that byproducts containing alkynyl can be avoided from being generated by isomerization in the reaction process, and the functionalization selectivity is further improved.

Description

Application of dinuclear amino acid-cobalt complex in catalysis of selective functionalization of diene C (sp 2) -H bond

Technical Field

The invention relates to the technical field of chemical catalysis, in particular to application of a dinuclear amino acid-cobalt complex in catalyzing selective functionalization of a binene C (sp ²) -H bond.

Background

A allene is an alkene compound containing a1, 2-allene group in which, of the three carbon atoms of the allene group, the middle sp hybridized carbon atom forms two mutually perpendicular pi orbitals with the terminal two sp ² hybridized carbon atoms. Selective functionalization of diene molecules is a subject of great research value in the synthesis of drug molecules and natural product functional molecules.

Because the three-carbon atom synthesis unit of the allene consists of accumulated double bonds, the two terminal carbon atoms of the allene are simultaneously connected with four substituent groups at most, the electron effect of the substituent groups on the terminal carbon can lead to different electron cloud densities of the three carbon atoms, meanwhile, the allene can generate products with various structures due to the space three-dimensional effect of the substituent groups and the influence of factors such as physical and chemical environments in a reaction system, and the like, so that the selectivity of target products is low, isomerization easily occurs in the reaction process, and alkynyl-containing byproducts are generated. In the current research on the diene selective functionalization, the problems of high reaction inertia, low selectivity and the like exist.

To solve these problems, researchers have provided a number of ideas, for example:

1. From the aspect of material structure, the functional group of electron withdrawing group is added to the allene to activate the material or the 1, 1-disubstituted allene is used, and the thinking is as follows:

2. From the aspect of reactivity, wang Yiming teaches developing a smart strategy to use cationic cyclopentadiene ion catalysts to increase site acidity of simple aliphatic dienes with the following ideas:

3. Professor Liu Guosheng and professor Wu Xinxin teach significant progress in the selective cyanation of dienes C (sp ²) -H using copper catalysts, the concept of which is shown below:

Although the above schemes have achieved significant results, these methods do not require the use of complex catalysts, stoichiometric oxidants or high temperatures. It remains tricky to design a universal and mild process to obtain products with unique site selectivity.

Disclosure of Invention

Based on the technical problems existing in the background technology, the invention provides application of a dinuclear amino acid-cobalt complex in catalyzing the selective functionalization of a binene C (sp ²) -H bond, creatively selects a mu-OH bridged binuclear amino acid-cobalt complex as a catalyst, contains a plurality of alkaline sites (such as hydroxyl, amino and the like), performs electrocatalytic hydrogen evolution reaction on the binene, can solve the problem of low activity and high selectivity of the binene reaction, and has good catalytic performance and good selectivity when the mu-OH bridged binuclear amino acid-cobalt complex is used for catalyzing the reaction of hydrogen on 1, 2-allene groups in the binene; in addition, the mu-OH bridged dinuclear amino acid-cobalt complex is matched with a proper reaction solvent, so that byproducts containing alkynyl can be avoided from being generated by isomerization in the reaction process, and the functionalization selectivity is further improved.

The invention provides an application of a mu-OH bridged dinuclear amino acid-cobalt complex in catalyzing selective functionalization of a diene C (sp ²) -H bond.

Preferably, the amino acid in the μ -OH bridged dinuclear amino acid-cobalt complex is an amino acid or a derivative thereof.

Preferably, the structure of the mu-OH bridged dinuclear amino acid-cobalt complex is as shown in formula (I):

r2 is H or R2 and R1 form a cyclic structure;

When R2 is H, R1 is one of H, alkyl, substituted alkyl, aryl, substituted aryl, indolyl, carboxyl, hydroxyl and amide;

The substituent in the substituted alkyl is one or more of hydroxyl, sulfhydryl, amino, guanidino, alkoxy, alkylthio, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl and O-doped unsaturated cycloalkyl;

The substituent in the substituted aryl is one or more of alkyl, hydroxyl, sulfhydryl, amino, guanidino, alkoxy, alkylthio, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl and O-doped unsaturated cycloalkyl.

Preferably, the triene is a trisubstituted triene, a1, 3-disubstituted triene or a1, 1-disubstituted triene.

Preferably, the structural formula of the 1, 3-disubstituted diene is shown as formula (II):

Wherein R3 and R4 are respectively and independently one of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl, alkenyl and cycloalkenyl;

The substituent groups in the substituted alkyl groups are as follows: alkenyl, alkynyl, hydroxy, mercapto, amino, ester, aryl, alkoxy, alkylthio, unsaturated alkoxy, unsaturated alkylthio, halogen, haloalkyl, haloalkoxy, haloalkylthio, halounsaturated alkoxy, halounsaturated alkylthio, hydroxyalkyl, hydroxyaryl, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl;

The substituent groups in the substituted cycloalkyl and substituted aryl are as follows: alkyl, alkenyl, alkynyl, hydroxyl, mercapto, amino, ester, phenyl, alkoxy, alkylthio, unsaturated alkoxy, unsaturated alkylthio, halogen, haloalkyl, haloalkoxy, haloalkylthio, halounsaturated alkoxy, halounsaturated alkylthio, hydroxyalkyl, hydroxyaryl, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl.

Preferably, R3 is not the same as R4.

Preferably, the 1, 3-disubstituted allenes comprise: One of the following; wherein X is halogen.

Preferably, the H with a small pKa of the C-H bond in C (sp ²) -H on the diene is selectively functionalized.

Preferably, the hydrogen on the ethylenic carbon remains in the structure of the 1, 2-allene group after selective functionalization.

Preferably, the functionalized functional group is

Wherein R5 is one of H, alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl and O-doped unsaturated cycloalkyl;

The substituent groups in the substituted cycloalkyl and substituted aryl are as follows: one or more of alkyl, alkenyl, alkynyl, hydroxyl, mercapto, amino, ester, phenyl, alkoxy, alkylthio, unsaturated alkoxy, unsaturated alkylthio, halogen, haloalkyl, haloalkoxy, haloalkylthio, halounsaturated alkoxy, halounsaturated alkylthio, hydroxyalkyl, hydroxyaryl, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl, phenyl-substituted amino groups, pinacol borate groups.

Preferably, when the functional group isWhen the product after hydrogen selective functional groups on the allene is an alpha-allenol.

Preferably, the method comprises the steps of,Comprising the following steps: One of the following; wherein X is halogen.

Preferably, the selective functionalization is carried out in an aprotic polar solvent.

Preferably, the selective functionalization is carried out by electrocatalysis in an aprotic polar solvent.

Preferably, the electrocatalytic is carried out in the presence of a nitroxide compound and an electrolyte.

Preferably, the molar ratio of the diene to the mu-OH bridged dinuclear amino acid-cobalt complex is 1:0.01-1.

Preferably, the aprotic polar solvent comprises: at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, 1, 3-dimethyl-tetrahydro-2-pyrimidinone, and hexamethylphosphoric triamide.

Preferably, the method comprises the steps of, the nitroxide radical compound is 2, 6-tetramethylpiperidine oxide, piperidinol oxide, 4-methoxy-TEMPO, 4-benzoyloxy-tetramethylpiperidine oxy radical, 4-oxy-TEMPO, 4-acetamido-2, 6-tetramethylpiperidine-1-oxy at least one of 4-carboxy-2, 6-tetramethylpiperidine 1-oxyl radical, 4-cyano-2, 6-tetramethylpiperidine 1-oxyl radical and 9-azabicyclo [3.3.1] nonane-N-oxyl radical.

Preferably, the electrolyte is at least one of tetraalkyl ammonium tetrafluoroborate, tetraalkyl ammonium hexafluorophosphate, tetraalkyl ammonium perchlorate.

Preferably, the molar ratio of the diene to the nitroxide compound is 1:0.01-1.

Preferably, the molar ratio of diene to electrolyte is 1:0.05-5.

Preferably, the temperature of the electrocatalysis is between-50 and 50 ℃.

Preferably, the electrocatalytic current is 1-1000mA.

The beneficial effects are that:

The invention creatively selects the mu-OH bridged binuclear amino acid-cobalt complex as a catalyst, contains a plurality of alkaline sites (such as hydroxyl, amino and the like), carries out electrocatalytic hydrogen evolution reaction on the allene, can solve the problem of high inertia and low selectivity of the allene reaction, has good catalytic performance when the mu-OH bridged binuclear amino acid-cobalt complex catalyzes hydrogen in C (sp ²) -H on the allene to react, has good selectivity, and has the product yield as high as 80 percent; in addition, the mu-OH bridged dinuclear amino acid-cobalt complex is matched with a proper reaction solvent, so that byproducts containing alkynyl can be prevented from being generated by isomerization in the reaction process, and the selectivity of functionalization is further improved;

The synthesis method of the mu-OH bridged dinuclear amino acid-cobalt complex is simple, low in cost and easy to obtain, can save cost, and solves the problems of complex and high cost of the existing catalyst used for diene selective functionalization. The electrocatalytic hydrogen evolution reaction is simple in operation and mild in reaction condition, can generate hydrogen, and can be used as clean fuel.

Drawings

FIGS. 1 to 7 show the nuclear magnetic patterns of the catalysts cat1 to cat7 in sequence.

FIGS. 8-23 show nuclear magnetic resonance hydrogen spectra of products 3a, 3g, 3i, 3r, 3v, 3x, 3ab, 3ae, 3al, 3ax, 3bd, 3ao, 3at, 3au, 3bg, 3bj in this order.

Detailed Description

The meaning of the above-mentioned selective functionalization of the dienic C (sp ²) -H bond is: the hydrogen in C (sp ²) -H on the allene is optionally substituted by a functional group.

The catalyst is a mu-OH bridged dinuclear amino acid-cobalt complex.

The inventor finds that from the perspective of organic synthesis, a plurality of selectable C (sp ²) -H reaction sites exist in the allene, and hydrogen evolution reaction can be carried out on the allene by selecting a proper catalyst to generate the allene carbanion with high regioselectivity, so that hydrogen selective functionalization on 1, 2-allene groups in the allene can be expected.

The hydrogen evolution reaction (HER-Hydrogen evolution reaction) can convert electrical energy into clean fuel hydrogen. HER catalysts are important materials for achieving hydrogen evolution reactions. However, direct catalytic organic conversion with HER catalysts has been less studied and the catalytic performance of HER catalysts in organic conversion has been elusive. In addition, the diene selective functionalization has the problems of high reaction inertia, low selectivity, easy isomerization, formation of alkynyl-containing byproducts and the like. It is therefore still difficult to choose which catalyst will increase the selectivity of the hydrogen functionalization on the 1, 2-propanediol groups in the diene and reduce the production of byproducts.

The inventor finds that the mu-OH bridged dinuclear amino acid-cobalt complex contains a plurality of basic sites (such as hydroxyl, amino and the like) and is used as a catalyst, and the hydrogen on 1, 2-allene groups in the allene can be selectively functionalized by adopting an electrocatalytic method, so that isomerization can be avoided to generate alkynyl-containing byproducts; in addition, the hydrogen evolution reaction can also generate hydrogen, and can be used as clean fuel.

The structural general formula of the amino acid is still remained in the derivatives of the amino acid, and the structural general formula of the amino acid is as follows: each amino acid molecule has an amino group and a carboxyl group linked to the same carbon atom.

The above amino acid or its derivative may be: isoleucine, valine, tertiary leucine, phenylalanine, histidine, proline, octahydro-1H-indole-2-carboxylic acid, glycine, methionine, 2-amino-4-hydroxybutyric acid, 2-amino-3-mercaptopropionic acid, 2-amino-5-guanidino valeric acid, 2-amino-4-carboxamido butyric acid and the like.

r2 is H or R2 and R1 form a cyclic structure;

The alkyl group may be an alkyl group having 1 to 8 carbon atoms; such as methyl, butyl, propyl, and the like.

The substituted alkyl and substituted aryl refer to an alkyl group and an aryl group with a substituent.

The substituted aryl group may be benzyl, 4-hydroxyphenyl, etc.

The amide group may be a carboxamide group, an acetamido group, a propionamide group, or the like.

The N-doped unsaturated cycloalkyl group may beEtc.

The R2 and R1 may form a single cyclic structure or may form a plurality of cyclic structures.

When R2 and R1 form a cyclic structure, the structural formula may be:

Etc.

When R2 is H, R1 is more preferably sec-butyl, tert-butyl, isopropyl, benzyl,One of them.

The preparation method of the mu-OH bridged dinuclear amino acid-cobalt complex comprises the following steps: taking amino acid or derivatives thereof, and reacting with cobalt salt and inorganic base in an organic solvent to obtain the mu-OH bridged dinuclear amino acid-cobalt complex.

In the preparation method of the mu-OH bridged dinuclear amino acid-cobalt complex, the cobalt salt is inorganic cobalt salt, and can be cobalt chloride, cobalt nitrate and the like; the inorganic base may be potassium hydroxide, sodium hydroxide, or the like; the organic solvent may be methanol, ethanol, etc.

In the preparation method of the mu-OH bridged dinuclear amino acid-cobalt complex, the reaction is carried out for 4 to 6 hours at room temperature.

In the preparation method of the mu-OH bridged dinuclear amino acid-cobalt complex, the molar ratio of the amino acid or the derivative thereof to the cobalt salt is 1:0.4-0.6, and the molar ratio of the amino acid or the derivative thereof to the inorganic base is 1:0.8-1.2.

The preparation method of the mu-OH bridged dinuclear amino acid-cobalt complex specifically comprises the following operations: adding amino acid or its derivative and inorganic base into organic solvent, mixing, dissolving, adding cobalt salt, reacting, and solid-liquid separating (such as suction filtration, centrifugation, etc.), and spin drying to obtain μ -OH bridged dinuclear amino acid-cobalt complex.

The mu-OH bridged dinuclear amino acid-cobalt complex can realize functionalization on hydrogen in C (sp ²) -H on mono-substituted biantene, di-substituted biantene and tri-substituted biantene.

The mu-OH bridged dinuclear amino acid-cobalt complex can realize selective functionalization on hydrogen in C (sp ²) -H on di-substituted biantene and tri-substituted biantene, and does not generate by-products containing alkynyl.

Preferably, the triene is a1, 3-trisubstituted triene, a1, 3-disubstituted triene or a1, 1-disubstituted triene; more preferably, the triene is a1, 3-disubstituted triene.

The structural formula of the 1, 3-trisubstituted diene can be as follows: Wherein R6 and R7 are respectively and independently alkyl, cycloalkyl and aryl. R6 and R7 may be the same or different.

The structural formula of the 1, 1-disubstituted allene can be as follows: Wherein R8, R9, R10 and R11 are respectively and independently alkyl, cycloalkyl and aryl. R8, R9, R10 and R11 may be the same or different.

The substituted alkyl, substituted cycloalkyl and substituted aryl refer to the substituent on the alkyl, cycloalkyl and aryl.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.

Preferably, R3 is not the same as R4.

Preferably, the 1, 3-disubstituted allenes comprise:

One of the following; wherein X is halogen.

Above-mentionedMeaning that hydrogen on any carbon atom in the thiophene can be substituted.

The inventor finds that under the action of the mu-OH bridged dinuclear amino acid-cobalt complex, during hydrogen evolution reaction, the functional group can selectively replace H with small pKa of a C-H bond in C (sp ²) -H on the diene, isomerization can not occur after substitution, an alkynyl-containing byproduct can not be generated, and the product still maintains the structure of the 1, 2-allene group. The inventors found that: under the electrocatalytic effect of the mu-OH bridged binuclear amino acid-cobalt complex, H with small pKa of C-H bond in C (sp ²) -H on diene is more acidic, the site is more easily dissociated to generate hydrogen evolution reaction with a substance, generated carbanion has extremely high reactivity, and the carbanion can quickly react with aldehyde generated by an anode after isomerization, so that the obtained product still remains 1, 2-allene groups, no alkynyl-containing byproducts are generated, and the reaction selectivity is high. This is not possible with conventional chemistry, which is generally performed by adding reagents in steps, so that the generated carbanion is easily isomerized and the reaction selectivity is low.

Preferably, the functionalized functional group is

The substituent groups in the substituted cycloalkyl and substituted aryl are as follows: one or more of alkyl, alkenyl, alkynyl, hydroxyl, mercapto, amino, ester, phenyl, alkoxy, alkylthio, unsaturated alkoxy, unsaturated alkylthio, halogen, haloalkyl, haloalkoxy, haloalkylthio, halounsaturated alkoxy, halounsaturated alkylthio, hydroxyalkyl, hydroxyaryl, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl, diphenylamino, pinacol borate groups.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms.

The pinacol borate group is abbreviated as-BPin.

The selective functionalization reaction is carried out using substance A with hydrogen in C (sp ²) -H on the diene.

When the structural formula of the substance A isIn this case, the functional group is/>Is a alpha-dienyl alcohol.

The mol ratio of the diene to the substance A is 1:0.1-3.0; more preferably, the molar ratio of diene to substance A is 1:1.0.

Preferably, the method comprises the steps of,Comprising the following steps:

One of the following; wherein X is halogen.

The inventor finds that the type of the solvent in the reaction has influence on whether isomerization occurs in the reaction process or whether byproducts containing alkynyl are generated or not; multiple experiments show that when the diene is electrically catalyzed in an aprotic polar solvent, hydrogen in C (sp ²) -H on the diene can be selectively functionalized, and isomerization and byproducts containing alkynyl can not occur.

The alkyl group in the tetraalkyl ammonium tetrafluoroborate, tetraalkyl ammonium hexafluorophosphate and tetraalkyl ammonium perchlorate may be an alkyl group having 1 to 8 carbon atoms or a benzyl group.

Preferably, the molar ratio of the diene to the nitroxide compound is 1:0.01-1.

Preferably, the molar ratio of diene to electrolyte is 1:0.05-5.

Preferably, the temperature of the electrocatalysis is between-50 and 50 ℃.

Preferably, the electrocatalytic current is 1-1000mA. Preferably the electrocatalytic time is 4 hours.

The anode of the electrocatalytic electrode can be carbon felt (GF), carbon rod, platinum, glassy carbon, reticular glassy carbon electrode (RVC), graphite flake, zinc and the like, and the cathode can be nickel (Ni), copper, platinum, iron, zinc, cobalt, gold, silver, carbon felt (GF), carbon rod, glassy carbon, reticular glassy carbon electrode (RVC) and the like.

The selective functionalization reaction of the hydrogen of the mu-OH bridged dinuclear amino acid-cobalt complex on the catalytic diene specifically comprises the following steps: uniformly mixing the diene, a substance A, mu-OH bridged binuclear amino acid-cobalt complex, an additive, an electrolyte and an aprotic polar solvent, inserting into a cathode sheet and an anode sheet, and electrifying to perform electrocatalytic reaction to obtain the functionalized diene.

In the electrocatalytic process, the generated hydrogen can be collected and used as clean fuel.

After the electrocatalytic reaction, the functionalized allene is proposed, and the specific steps are as follows: after the electrocatalytic reaction is finished, adding water and ethyl acetate for extraction, taking an organic phase for column chromatography, collecting eluent, and removing a solvent to obtain functionalized allene.

The technical scheme of the invention is described in detail through specific embodiments.

Example 1

A preparation method of a mu-OH bridged dinuclear amino acid-cobalt complex comprises the following steps: 2.0mmol of amino acid or its derivative and 2.0mmol of potassium hydroxide are added into a clean round bottom flask, and then 10mL of methanol is added, and the mixture is stirred and mixed until the amino acid or its derivative is completely dissolved and is clear and transparent; then adding 1.0mmol of cobalt chloride, stirring for 5 hours at normal temperature and normal pressure, filtering, taking filtrate, and spin-drying to obtain the mu-OH bridged dinuclear amino acid-cobalt complex.

7 Amino acids or derivatives thereof (isoleucine, valine, tertiary leucine, phenylalanine, histidine, proline and octahydro-1H-indole-2-carboxylic acid) with different structures can be selected to obtain 7 mu-OH bridged dinucleotide-cobalt complexes, the structural formulas of which are shown below, and are respectively abbreviated as catalysts cat1-cat7, wherein ^s Bu is sec-butyl, ⁱ Pr is isopropyl, ^t Bu is tertiary butyl and Bn is benzyl:

the nuclear magnetic patterns of the catalyst cat1-cat7 are shown in figures 1-7 in sequence.

Example 2

The catalyst cat1 catalyzes the selective functionalization of the hydrogen on the diene, and the reaction formula is shown below:

The method specifically comprises the following steps:

Into a dry and clean reaction tube, 0.5mmol of diene 1a, 0.5mmol of benzyl alcohol 2a, 0.025mmol of catalyst cat1, 0.1mmol of additive 2, 6-tetramethylpiperidine oxide (TEMPO), 0.5mmol of electrolyte tetrabutylammonium tetrafluoroborate (ⁿBu₄NBF₄) and 10mL of N, N-dimethylformamide are added and stirred and mixed uniformly; then inserting an electrode plate, wherein an anode is made of carbon felt (GF), a cathode is made of iron plate (Fe), and then carrying out 10mA constant-current electrocatalytic reaction for 4 hours at 40 ℃;

the reaction was completed by detecting the reaction liquid with TLC plate, then adding water and ethyl acetate, extracting, eluting with an organic phase by column chromatography, collecting the eluent, and removing the solvent to obtain the α -dienyl alcohol product 3a having a yield of 80% and a purity of 99.9% and free of alkynyl-containing byproducts.

FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of the product 3 a.

Example 3

Catalyst cat1 was replaced by catalyst cat2-cat7, respectively, prepared as in example 2, each giving product 3a; the yields of catalyst cat2-cat7 are 78%, 68%, 25%, 27%, 71%, 53% in sequence, the purity reaches 99.9%, and no by-product containing alkynyl exists.

Example 4

N, N-dimethylformamide is replaced by N, N-dimethylacetamide and dimethyl sulfoxide respectively, and the products 3a can be obtained by respectively preparing the N, N-dimethylformamide and the dimethyl sulfoxide according to the method of the example 2; the corresponding yields are 58% and 25% in sequence; the purity of the product reaches 99.9%, and the product does not contain alkynyl byproducts.

Example 5

Respectively replacing tetrabutylammonium tetrafluoroborate with tetrabutylammonium hexafluorophosphate and tetrabutylammonium perchlorate, and respectively preparing the same according to the method of the example 2 to obtain a product 3a; the corresponding yields are 15% and 50% in sequence; the purity of the product reaches 99.9%, and the product does not contain alkynyl byproducts.

Comparative example 1

Adding 0.5mmol of diene 1a, 0.5mmol of benzyl alcohol 2a and 0.75mmol of n-butyllithium catalyst into a dry and clean reaction tube at the temperature of minus 20 ℃, and stirring and uniformly mixing; the reaction is kept at the temperature for 4 hours, the TLC plate is used for detecting the reaction liquid to determine the end of the reaction, then water and ethyl acetate are added for extraction, the organic phase is taken for column chromatography elution, the eluent is collected, the solvent is removed, and the alpha-dienyl alcohol product 3a is obtained, and the yield is 58%; the purity is 50.0%, the impurity is more, and the byproduct containing alkynyl is provided.

Comparative example 2

Cobalt chloride is replaced by nickel chloride, and a mononuclear amino acid-nickel complex is prepared by the method of example 1 with isoleucine, and the structural formula of the mononuclear amino acid-nickel complex is shown as follows:

Product 3a was prepared by the method of example 2, substituting catalyst cat1 with a mononuclear amino acid-nickel complex; the yield thereof was found to be 24%; the purity is 80%, the impurities are more, and the byproducts containing alkynyl are provided.

Example 6

The procedure of example 2 was followed except that different structures of the diene and substance A were chosen to produce the product, the results of which are shown in Table 1.

TABLE 1

/>

Remarks: the products in Table 1 all reached 99.9% purity and were free of alkynyl-containing by-products.

FIGS. 8-23 show nuclear magnetic resonance hydrogen spectra of products 3g, 3i, 3r, 3v, 3x, 3ab, 3ae, 3al, 3ax, 3bd, 3ao, 3at, 3au, 3bg, 3bj in this order.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims

1. Use of a mu-OH bridged dinuclear amino acid-cobalt complex for catalyzing the selective functionalization of a binene C (sp ²) -H bond.

2. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 1 for the catalytic binalkene C (sp ²) -H bond selective functionalization, wherein the amino acid in the μ -OH bridged dinuclear amino acid-cobalt complex is an amino acid or a derivative thereof; preferably, the structure of the mu-OH bridged dinuclear amino acid-cobalt complex is as shown in formula (I):

r2 is H or R2 and R1 form a cyclic structure;

3. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 1 or 2 for the catalytic C (sp ²) -H bond selective functionalization of a triene, characterized in that the triene is a trisubstituted triene, a 1, 3-disubstituted triene or a 1, 1-disubstituted triene; preferably, the structural formula of the 1, 3-disubstituted diene is shown as formula (II):

The substituent groups in the substituted cycloalkyl and substituted aryl are as follows: one or more of alkyl, alkenyl, alkynyl, hydroxyl, mercapto, amino, ester, phenyl, alkoxy, alkylthio, unsaturated alkoxy, unsaturated alkylthio, halogen, haloalkyl, haloalkoxy, haloalkylthio, halounsaturated alkoxy, halounsaturated alkylthio, hydroxyalkyl, hydroxyaryl, cycloalkyl, N-doped cycloalkyl, S-doped cycloalkyl, O-doped cycloalkyl, unsaturated cycloalkyl, N-doped unsaturated cycloalkyl, S-doped unsaturated cycloalkyl, O-doped unsaturated cycloalkyl; preferably, R3 is not the same as R4.

4. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 3 for the catalytic binaphthyl C (sp ²) -H bond selective functionalization, wherein the 1, 3-disubstituted biantene comprises:

One of the following; wherein X is halogen.

5. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to any one of claims 1 to 4 for the catalytic selective functionalization of the C (sp ²) -H bond of dienes, characterized in that the selective functionalization of H with a small pKa of the C-H bond in C (sp ²) -H on the diene is performed; preferably, the hydrogen on the ethylenic carbon remains in the structure of the 1, 2-allene group after selective functionalization.

6. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to any one of claims 1 to 5 for the catalytic bialkene C (sp ²) -H bond selective functionalization, characterized in that the functionalized functional group is

7. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 6 for the catalytic bialkene C (sp ²) -H bond selective functionalization, wherein when the functional group isWhen the product after hydrogen selective functional groups on the allene is alpha-allenol; preferably,/>Comprising the following steps: /(I)

One of the following; wherein X is halogen.

8. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to any one of claims 1 to 7 for the catalytic biantene C (sp ²) -H bond selective functionalization, characterized in that the selective functionalization is carried out in an aprotic polar solvent; preferably, the selective functionalization is carried out by electrocatalysis in an aprotic polar solvent; preferably, the electrocatalytic is carried out in the presence of a nitroxide compound and an electrolyte; preferably, the molar ratio of the diene to the mu-OH bridged dinuclear amino acid-cobalt complex is 1:0.01-1.

9. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 8 for the catalytic biantene C (sp ²) -H bond selective functionalization, wherein the aprotic polar solvent comprises: at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, 1, 3-dimethyl-tetrahydro-2-pyrimidinone, hexamethylphosphoric triamide; preferably, the method comprises the steps of, the nitroxide radical compound is 2, 6-tetramethylpiperidine oxide, piperidinol oxide, 4-methoxy-TEMPO, 4-benzoyloxy-tetramethylpiperidine oxy radical, 4-oxy-TEMPO, 4-acetamido-2, 6-tetramethylpiperidine-1-oxy at least one of 4-carboxy-2, 6-tetramethylpiperidine 1-oxyl radical, 4-cyano-2, 6-tetramethylpiperidine 1-oxyl radical, 9-azabicyclo [3.3.1] nonane-N-oxyl radical; preferably, the electrolyte is at least one of tetraalkyl ammonium tetrafluoroborate, tetraalkyl ammonium hexafluorophosphate, tetraalkyl ammonium perchlorate.

10. Use of a μ -OH bridged dinuclear amino acid-cobalt complex according to claim 8 or 9 for the catalysis of the selective functionalization of the allene C (sp ²) -H bond, characterized in that the molar ratio of allene to nitroxide compound is 1:0.01-1; preferably, the molar ratio of the diene to the electrolyte is 1:0.05-5; preferably, the temperature of the electrocatalysis is-50-50 ℃; preferably, the electrocatalytic current is 1-1000mA.