KR102220378B1 - N-heterocyclic transition metal complex catalyst and preparing method thereof - Google Patents

Abstract

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[화학식 2]

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(상기 화학식 1 및 화학식 2 에서, R¹ 내지 R¹⁰ 은, 각각 독립적으로, 수소, 치환될 수 있는 C₁-C₆ 의 사슬형 포화 탄화수소, 치환될 수 있는 C_3-C₆ 의 가지달린 사슬형 포화 탄화수소, 치환될 수 있는 C₆-C₈의 아릴, 치환될 수 있는 5-원 불포화 또는 방향족 고리, 치환될 수 있는 6-원 불포화 또는 방향족 고리로 이루어진 군으로부터 선택되는 1개 이상의 고리이고, M 은 Cu 이고, Ar 은 치환될 수 있는 5-원 불포화 또는 방향족 고리, 치환될 수 있는 6-원 불포화 또는 방향족 고리, 치환될 수 있는 5-원 불포화 또는 방향족 헤테로 고리 및 치환될 수 있는 6-원 불포화 또는 방향족 헤테로 고리로 이루어진 군으로부터 선택되는 1 개 이상의 고리이고, 상기 헤테로 고리는 S, N, O 및 이들의 조합들로 이루어진 군으로부터 선택된 하나 이상을 포함하며, 상기 치환은 C₁-C₆ 의 알킬 또는 C₆-C₈ 의 아릴에 의해 치환되는 것임).It relates to an N-heterocyclic transition metal complex catalyst represented by the following Formula 1 or Formula 2:
[Formula 1]

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[Formula 2]

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(In Formulas 1 and 2, R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain At least one ring selected from the group consisting of a saturated hydrocarbon, a substituted C ₆ -C ₈ aryl, a substituted 5-membered unsaturated or aromatic ring, and a substituted 6-membered unsaturated or aromatic ring, , M is Cu, Ar is a 5-membered unsaturated or aromatic ring that may be substituted, a 6-membered unsaturated or aromatic ring that may be substituted, a 5-membered unsaturated or aromatic hetero ring that may be substituted, and 6 -One or more rings selected from the group consisting of unsaturated or aromatic heterocycles, the hetero ring includes at least one selected from the group consisting of S, N, O and combinations thereof, and the substitution is C _1- It will be substituted by a C ₆ alkyl or C ₆ -C ₈ aryl).

Description

N-heterocyclic transition metal complex catalyst and its manufacturing method {N-HETEROCYCLIC TRANSITION METAL COMPLEX CATALYST AND PREPARING METHOD THEREOF}

The present application relates to an N-heterocyclic transition metal complex catalyst and a method for preparing the same.

The carbon-hydrogen bonding reaction using a copper-hydride (Cu-H) catalyst is one of very important reactions in the field of organic synthesis. Reactions using such catalysts include conjugate reduction reactions and hydroboration reactions.In particular, borohydride addition reactions can easily produce organic boron compounds having various applications in organic chemistry and industrial fields. It can be synthesized.

In modern chemistry, reactions using copper-hydride catalysts began in 1988 with the development of Stryker's reagent. However, since the striker reagent is very unstable in the air, it is difficult to handle and store. In the early 2000s, a catalyst was developed in which an N-heterocyclic carbine (NHC) ligand was coordinated with copper, and a copper-hydride catalyst was easily formed by adding a base and silane to the catalyst. It can be synthesized. However, the base mainly used in the reaction cannot be stored for a long time in the air, and there is a disadvantage that a base sensitive starting material cannot be used. Therefore, there is a need to develop a technology that is stable in air and reacts with silane or hydrogen without a base to easily synthesize a copper-hydride catalyst.

Korean Patent Registration No. 10-0797241, which is the background technology of the present application, relates to an organometallic catalyst composition. The above registered patent is a catalyst composition useful for producing a polymer by polymerizing at least one monomer, wherein the catalyst composition comprises a post-contact organometallic compound, a post-contact organoaluminum compound, and a post-contact fluorinated solid oxide compound. Is being disclosed.

The present application is to solve the problems of the prior art described above, and an object of the present invention is to provide an N-heterocyclic transition metal complex catalyst and a method for preparing the same.

However, the technical problems to be achieved by the embodiments of the present application are not limited to the technical problems as described above, and other technical problems may exist.

As a technical means for achieving the above technical problem, the first aspect of the present application provides an N-heterocyclic transition metal complex catalyst represented by the following Chemical Formula 1 or Chemical Formula 2:

[Formula 1]

;

[Formula 2]

;

;

(In Chemical Formula 1 and Chemical Formula 2,

R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C ₆ -C ₈ aryl, 5-membered unsaturated or aromatic ring which may be substituted, 6-membered unsaturated or aromatic ring that may be substituted, is at least one ring selected from the group consisting of, M is Cu, Ar is substituted Consisting of a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted, and a 6-membered unsaturated or aromatic hetero ring which may be substituted At least one ring selected from the group, the hetero ring includes at least one selected from the group consisting of S, N, O and combinations thereof, and the substitution is C ₁ -C ₆ alkyl or C ₆ -C ₈ is substituted by aryl).

According to one embodiment of the present application, the R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, a C ₃ C ₆ branched chain saturated hydrocarbon, and M is Cu, and Ar is a 5-membered aromatic hetero ring, and the hetero ring may include at least one selected from the group consisting of S, N, and combinations thereof, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, the N-heterocyclic transition metal complex catalyst may be to synthesize an organic boron compound as a catalyst for the borohydride addition reaction, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, the N-heterocyclic transition metal complex catalyst may include any one of the following compounds, but is not limited thereto:

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In the second aspect of the present application, in the method for preparing an N-heterocyclic transition metal complex catalyst according to the first aspect of the present application, reacting a compound represented by the following Formula 3 or Formula 4 with a compound represented by the following Formula 5 It provides a method for preparing an N-heterocyclic transition metal complex catalyst comprising:

[Formula 3]

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;

[Formula 4]

;

;

[Formula 5]

;

;

(In Chemical Formulas 3 to 5,

R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C ₆ -C ₈ aryl, 5-membered unsaturated or aromatic ring which may be substituted, 6-membered unsaturated or aromatic ring that may be substituted, is at least one ring selected from the group consisting of, M is Cu, Ar is substituted Consisting of a 5-membered unsaturated or aromatic ring that may be substituted, a 6-membered unsaturated or aromatic ring that may be substituted, a 5-membered unsaturated or aromatic hetero ring that may be substituted, and a 6-membered unsaturated or aromatic hetero ring that may be substituted At least one ring selected from the group, the hetero ring includes at least one selected from the group consisting of S, N, O and combinations thereof, and the substitution is C ₁ -C ₆ alkyl or C ₆ -C ₈ is substituted by aryl).

According to one embodiment of the present application, the R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, a C ₃ C ₆ branched chain saturated hydrocarbon, and M is Cu, and Ar is a 5-membered aromatic hetero ring, and the hetero ring may include at least one selected from the group consisting of S, N, and combinations thereof, but is not limited thereto.

The above-described problem solving means are merely exemplary and should not be construed as limiting the present application. In addition to the above-described exemplary embodiments, additional embodiments may exist in the drawings and detailed description of the invention.

According to the above-described problem solving means of the present application, the N-heterocyclic transition metal complex catalyst according to the present application includes Ar, which is a 5-membered aromatic hetero ring, and the hetero ring includes S, so that stability during storage of the catalyst can be improved. have. Specifically, when Ar includes a 5-membered aromatic hetero ring, the N-heterocyclic transition metal complex catalyst can be stored at room temperature and can be stored without a special container.

In addition, when the N-heterocyclic transition metal complex catalyst according to the present application includes a 5-membered aromatic hetero ring, the hetero ring is easily separated without a base in the catalyst activation step, so that the catalyst is not used without a base. There is an advantage that can be easily synthesized.

Further, the N-heterocyclic transition metal complex catalyst according to the present application can efficiently synthesize an organic boron compound even in a small amount in the borohydride addition reaction.

However, the effect obtainable in the present application is not limited to the effects as described above, and other effects may exist.

Hereinafter, exemplary embodiments of the present application will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present application. However, the present application may be implemented in various different forms and is not limited to the embodiments described herein. In addition, in the drawings, parts not related to the description are omitted in order to clearly describe the present application, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is said to be "connected" with another part, this includes not only the case that it is "directly connected", but also the case that it is "electrically connected" with another element interposed therebetween. do.

Throughout this specification, when a member is positioned "on", "upper", "upper", "under", "lower", and "lower" of another member, this means that a member is located on another member. It includes not only the case where they are in contact but also the case where another member exists between the two members.

Throughout the specification of the present application, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

As used herein, the terms "about", "substantially" and the like are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and to aid understanding of the present application In order to prevent unreasonable use by unscrupulous infringers of the stated disclosures, either exact or absolute figures are used. In addition, throughout the specification of the present application, "step to" or "step of" does not mean "step for".

In the entire specification of the present application, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Makushi format, and the component It means to include one or more selected from the group consisting of.

Throughout this specification, the description of "A and/or B" means "A or B, or A and B".

Hereinafter, the N-heterocyclic transition metal complex catalyst of the present application and a method for preparing the same will be described in detail with reference to Examples and Examples. However, the present application is not limited to these embodiments and examples.

As a technical means for achieving the above technical problem, the first aspect of the present application provides an N-heterocyclic transition metal complex catalyst represented by the following Chemical Formula 1 or Chemical Formula 2:

[Formula 1]

;

;

[Formula 2]

;

;

(In Chemical Formula 1 and Chemical Formula 2,

R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C ₆ -C ₈ aryl, 5-membered unsaturated or aromatic ring which may be substituted, 6-membered unsaturated or aromatic ring that may be substituted, is at least one ring selected from the group consisting of, M is Cu, Ar is substituted Consisting of a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted, and a 6-membered unsaturated or aromatic hetero ring which may be substituted At least one ring selected from the group, the hetero ring includes at least one selected from the group consisting of S, N, O and combinations thereof, and the substitution is C ₁ -C ₆ alkyl or C ₆ -C ₈ is substituted by aryl).

According to one embodiment of the present application, the R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, a C ₃ C ₆ branched chain saturated hydrocarbon, and M is Cu, and Ar is a 5-membered aromatic hetero ring, and the hetero ring may include at least one selected from the group consisting of S, N, and combinations thereof, but is not limited thereto.

The M may be Cu, which can save cost by using inexpensive copper (Cu) instead of rare and expensive platinum (Pt) used in the prior art.

In addition, Ar is a 5-membered aromatic hetero ring, and the hetero ring may include S, which may improve stability during storage of the catalyst. Specifically, when Ar includes a 5-membered aromatic hetero ring, the N-heterocyclic transition metal complex catalyst can be stored at room temperature and can be stored without a special container.

In addition, when Ar contains a 5-membered aromatic hetero ring, since the hetero ring is easily separated without a base in the catalyst activation step, there is an advantage that the catalyst can be easily synthesized without the use of a base. .

According to the exemplary embodiment of the present disclosure, the N-heterocyclic transition metal complex catalyst may be to synthesize an organic boron compound as a catalyst for the borohydride addition reaction, but is not limited thereto. The N-heterocyclic transition metal complex catalyst can efficiently synthesize an organic boron compound even in a small amount in the borohydride addition reaction.

According to the exemplary embodiment of the present disclosure, the N-heterocyclic transition metal complex catalyst may include any one of the following compounds, but is not limited thereto:

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In the second aspect of the present application, in the method for preparing an N-heterocyclic transition metal complex catalyst according to the first aspect of the present application, reacting a compound represented by the following Formula 3 or Formula 4 with a compound represented by the following Formula 5 It provides a method for preparing an N-heterocyclic transition metal complex catalyst comprising:

[Formula 3]

;

;

[Formula 4]

;

;

[Formula 5]

;

;

(In Chemical Formulas 3 to 5,

R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C ₆ -C ₈ aryl, 5-membered unsaturated or aromatic ring which may be substituted, 6-membered unsaturated or aromatic ring that may be substituted, is at least one ring selected from the group consisting of, M is Cu, Ar is substituted Consisting of a 5-membered unsaturated or aromatic ring which may be substituted, a 6-membered unsaturated or aromatic ring which may be substituted, a 5-membered unsaturated or aromatic hetero ring which may be substituted, and a 6-membered unsaturated or aromatic hetero ring which may be substituted At least one ring selected from the group, the hetero ring includes at least one selected from the group consisting of S, N, O and combinations thereof, and the substitution is C ₁ -C ₆ alkyl or C ₆ -C ₈ is substituted by aryl).

With respect to the manufacturing method of the N-heterocyclic transition metal complex catalyst according to the second aspect of the present application, detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, but even if the description is omitted, the first aspect of the present application The described content can be equally applied to the second aspect of the present application.

A catalyst in which a conventional N-heterocyclic carbine (NHC) ligand is coordinated with copper can easily synthesize a copper-hydride catalyst by adding a base and silane. However, there is a disadvantage that the base mainly used in the reaction cannot be stored for a long time in the air, and the base sensitive starting material cannot be used. The present inventors have recognized this problem and have developed a method for preparing an N-heterocyclic transition metal complex catalyst that is stable in air and can easily synthesize a catalyst without the use of a base.

According to one embodiment of the present application, the R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, a C ₃ C ₆ branched chain saturated hydrocarbon, and M is Cu, and Ar is a 5-membered aromatic hetero ring, and the hetero ring may include at least one selected from the group consisting of S, N, and combinations thereof, but is not limited thereto.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[Example]

Example 1: Preparation of (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-yl)(thiophene-2-carbonyl)oxy) copper

Example 1-(1): Preparation of 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazole-3-ium-2-ide

In a glove box filled with argon, 1,3-bis-(2,6-diisopropylphenyl)imidazolium chloride compound (213.5 mg, 0.5 mmol) and KOt-Bu (61.7 mg, 0.55 mmol) were added to a Schrank flask. Dissolved in THF solvent (3 mL) and stirred at room temperature for 4 hours. After completion of the reaction, the sample was filtered through Celite under toluene and dried under vacuum. The concentrated carbene was used in the next reaction without purification.

Example 1-(2): Preparation of (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-yl)(thiophene-2-carbonyl)oxy) copper

Toluene (6 mL) and copper(I)thiophene-2-carboxylate (CuTC, 95.3 mg, 0.5 mmol) were added to the concentrated carbene compound 4, followed by stirring at room temperature for 16 hours. The solid material remaining after 16 hours was washed with dichloromethane solvent. And the precipitate was washed again with hexane solvent, and Example 1 (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-yl)(thiophene-2-carbonyl)oxy ) Copper (SIPr-CuTC) was obtained as a white solid (206 mg, 71% yield).

¹ H-NMR (500 MHz, CDCl ₃ ) δ7.41(t, J =8.0 Hz,2H),7.31(d, J =2.5 Hz,1H),7.26(d, J =8.0 Hz,4H),7.13 (d, J =4.5 Hz,1H),6.81(dd, J =4.5,2.5 Hz,1H),4.04(s,4H),3.13-3.05 (m, 4H), 1.39 (d, J =7.0 Hz, 12H), 1.35 (d, J =7.0 Hz, 12H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ 203.2,167.0,146.7,141.7,134.5,130.2,129.9,128.6,126.8,124.6,53.8,29.0,25.4,24.0.

The synthesized Example 1 was subjected to X-ray diffraction studies by obtaining crystals in dichloromethane and pentane solvents, and the results are as follows (Found: C, 66.36; H, 6.82; N, 4.74; S, 5.41%) Calc. for C ₃₂ H ₄₁ CuN ₂ O ₂ S:C,66.12; H,7.11;N,4.82;S,5.52%).

Example 2: (1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazol-2-yl)(thiophene-2-carbonyl)oxy) of copper Produce

Example 2-(1): Preparation of 1,3-bis(2,6-diisopropylphenyl)-1H-imidazole-3-ium-2-ide

In a glove box filled with argon, 1.3-bis-(2,6-diisopropylphenyl)imidazolium chloride compound (212.5 mg, 0.5 mmol) and KO t -Bu (61.7 mg, 0.55 mmol) were added to a Schlenk flask. It was dissolved in THF solvent (3 mL) and stirred at room temperature for 4 hours. After completion of the reaction, the sample was filtered through Celite under toluene and dried under vacuum. The concentrated carbene was used in the next reaction without purification.

Example 2-(2): (1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazol-2-yl) (thiophene-2-carbonyl) Preparation of oxy) copper

Toluene (6 mL) and copper(I)thiophene-2-carboxylate (CuTC, 95.3 mg, 0.5 mmol) were added to the concentrated carbene compound, followed by stirring at room temperature for 16 hours. The solid material remaining after 16 hours was washed with dichloromethane solvent. And the precipitate was washed again with a normal hexane solvent to give Example 2 (1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazol-2-yl)( Thiophene-2-carbonyl)oxy) copper (IPr-CuTC) was obtained as a white solid (2526 mg, 87% yield).

¹ H-NMR (500 MHz, CDCl3) δ7.50(t,J=8.0 Hz,2H),7.37(d,J=3.5 Hz,1H),7.31(d,J=8.0 Hz,4H),7.15( s,2H),7.14(d,J=5.0 Hz,1H),6.83(dd,J=5.0,3.5 Hz,1H),2.64-2.56 (m, 4H), 1.32 (d,J=7.0 Hz,12H ), 1.23 (d, J=7.0 Hz, 12H); ¹³ C-NMR (125 MHz, CDCl3) δ 180.3,167.1,145.6,141.6,134.6,130.5,130.3,128.6,126.9,124.3,123.3,28.8,24.7,24.0.

[Experimental Example]

Using an N-heterocyclic transition metal complex catalyst, a boron hydride reaction was carried out with 8a and 8b boron substrates on the terminal alkyne. Various reactivity was shown according to the type of N-heterocyclic transition metal complex catalyst, and SIPr-CuOAC (Comparative Example 2) and copper (II) of copper (I), an N-heterocyclic transition metal complex catalyst used as a comparative example, Compared to IPr-Cu(OAc) ₂ (Comparative Example 1), the SIPr-CuTC compound of Example 1 showed a higher yield.

[Table 1]

^a _{Measured by 1} H-NMR spectroscopy using N,N -dimethylformamide as an internal standard. ^b Purified yield. ^c Response time 24 hours. ^d Yield containing 9-Bdan and 10-Bdan compounds. ^e 1 mol% of the catalyst was used. The borohydride reaction was carried out on various types of terminal alkyl compounds using the SIPr-CuTC catalyst of Example 1.

SIPr-CuTC (1 mol% to 5 mol%, 0.005 mmol or 0.025 mmol) of Example 1 was dissolved in toluene (3 mL) in a Schrank flask in a nitrogen atmosphere. HBpin or HBdan (1.2 equivalent, 0.6 mmol) was added to the reaction and stirred at room temperature for 15 minutes. Toluene (3 mL) was added to dissolve the terminal alkyne sample 7 (1 equivalent, 0.5 mol). The state of the reactants was confirmed using thin layer chromatography (TLC) at room temperature. After completion of the reaction, the reaction product was filtered through Celite and concentrated. The reaction product was purified using silica gel.

According to the general experimental method presented in the reaction scheme, a yellow solid sample, (E)-2-styryl-2,3-dihydro-1H-naphtho[1,3,2]diazaborinine compound 9a-Bdan compound Was synthesized in 82% yield.

¹ H-NMR (500 MHz, CDCl3) δ7.53-7.52 (m, 2H), 7.41-7.38 (m, 2H), 7.34-7.32 (m, 1H), 7.17-7.12 (m, 3H), 7.06- 7.04 (m, 2H), 6.37 (d, J = 7.0 Hz, 2H), 6.33 (d, J = 18.5 Hz, 1H), 5.85 (brs, 2H); ¹³ C-NMR (125 MHz, CDCl3) δ 143.7,141.2,137.6,136.4,128.7,127.6,126.8,119.9,117.7,105.8.

In addition, according to the general experimental method presented in the reaction scheme, a colorless liquid sample (E)-2-(3-(benzyloxy)prop-1-en-1-yl)-2,3-dihydro-1H- Naphtho[1,8-de][1,3,2]diazaborinine compound 9a-Bpin was synthesized in 98% yield.

¹ H-NMR (500 MHz, CDCl3) δ7.50-7.48 (m, 2H), 7.40 (d, J=18.5 Hz,1H), 7.35-7.28 (m, 3H), 6.17 (d, J=18.5 Hz ,1H),1.32(s,12H); ¹³ C-NMR (125 MHz, CDCl3) δ 149.5, 137.5, 128.9, 128.6, 127.1, 83.4, 24.8.

In addition, as a result of performing the reaction at room temperature for 2 hours on a 20 mmol scale according to the general experimental method presented in the reaction scheme, (E)-2-(3-(benzyloxy)prop-1-ene-1 -Yl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine compound 9a-Bpin was synthesized in 96% yield (4.40 g).

The stereoselective boron hydride reaction of terminal alkynes using a stable N-heterocyclic carbene-copper thiophene-2-carboxylic acid (CuTC) complex in air is performed by pinacolborane (HBpin) or 1,8-naphthalenediaminapto I tried to proceed with the reaction with Borein (HBdan). The newly synthesized complex can be directly activated by hydroborane without a cocatalyst such as a base, and shows high reactivity to alkyne borohydride reaction under mild conditions. The gram-scale borohydride reaction of the terminal phenyl acetylene demonstrated the efficiency for the synthesis of alkenyl boron compounds.

The foregoing description of the present application is for illustrative purposes only, and those of ordinary skill in the art to which the present application pertains will be able to understand that it is possible to easily transform it into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present application is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present application.

Claims (6)

In the N-heterocyclic transition metal complex catalyst represented by the following Formula 1 or Formula 2,
The N-heterocyclic transition metal complex catalyst is to synthesize an organic boron compound as a catalyst for the borohydride addition reaction, an N-heterocyclic transition metal complex catalyst:
[Formula 1]

;
[Formula 2]

;
(In Chemical Formula 1 and Chemical Formula 2,
R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C _{At least one ring selected from the group consisting of a 6-} C ₈ aryl, a substituted 5-membered unsaturated or aromatic ring, and a substituted 6-membered unsaturated or aromatic ring,
M is Cu,
Ar is a 5-membered unsaturated or aromatic ring that may be substituted, a 6-membered unsaturated or aromatic ring that may be substituted, a 5-membered unsaturated or aromatic hetero ring that may be substituted, and a 6-membered unsaturated or aromatic hetero that may be substituted It is one or more rings selected from the group consisting of rings,
The hetero ring includes one or more selected from the group consisting of S, N, O, and combinations thereof,
The substitution is to be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₈ aryl).
The method of claim 1,
The R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, and a C ₃ -C ₆ branched chain saturated hydrocarbon,
M is Cu,
Ar is a 5-membered aromatic hetero ring,
The hetero ring is to include one or more selected from the group consisting of S, N and combinations thereof,
N-heterocyclic transition metal complex catalyst.
delete The method of claim 1,
The N-heterocyclic transition metal complex catalyst comprises any one of the following compounds, an N-heterocyclic transition metal complex catalyst:

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In the method for preparing an N-heterocyclic transition metal complex catalyst according to any one of claims 1, 2 and 4,
A method of preparing an N-heterocyclic transition metal complex catalyst comprising reacting a compound represented by the following Formula 3 or Formula 4 with a compound represented by the following Formula 5:
[Formula 3]

;
[Formula 4]

;
[Formula 5]

;
(In Formulas 3 to 5,
R ¹ to R ¹⁰ are each independently hydrogen, a substituted C ₁ -C ₆ chain saturated hydrocarbon, a substituted C ₃ -C ₆ branched chain saturated hydrocarbon, and a substituted C _{At least one ring selected from the group consisting of a 6-} C ₈ aryl, a substituted 5-membered unsaturated or aromatic ring, and a substituted 6-membered unsaturated or aromatic ring,
M is Cu,
Ar is a 5-membered unsaturated or aromatic ring that may be substituted, a 6-membered unsaturated or aromatic ring that may be substituted, a 5-membered unsaturated or aromatic hetero ring that may be substituted, and a 6-membered unsaturated or aromatic hetero that may be substituted It is one or more rings selected from the group consisting of rings,
The hetero ring includes one or more selected from the group consisting of S, N, O, and combinations thereof,
The substitution is to be substituted by C ₁ -C ₆ alkyl or C ₆ -C ₈ aryl).
The method of claim 5,
The R ¹ to R ¹⁰ are each independently hydrogen, a C ₁ -C ₆ chain saturated hydrocarbon, and a C ₃ -C ₆ branched chain saturated hydrocarbon,
M is Cu,
Ar is a 5-membered aromatic hetero ring,
The hetero ring is to include one or more selected from the group consisting of S, N and combinations thereof,
Method for producing an N-heterocyclic transition metal complex catalyst.