JPWO2016143868A1 - Polymer transition metal complex, production method thereof and use thereof - Google Patents

Abstract

The present invention relates to a polymer transition metal complex represented by the following general formula (2), a production method thereof and use as a catalyst. In the formula (2), is an aromatic hydrocarbon group or an aromatic heterohydrocarbon group, R 1, R 2, R 3, R 4 are linear or cross-linked polystyrene chains, and the cross-linked polystyrene chain is represented by the formula (2) At least one bisphosphine unit represented by 3) can be contained. M is a transition metal or a transition metal ion that can have a ligand.

Description

The present invention relates to a polymer transition metal complex, a production method thereof and use thereof.
This application claims the priority of Japanese Patent Application No. 2015-046761 filed on Mar. 10, 2015, the entire description of which is specifically incorporated herein by reference.

  The organic polymer-supported phosphine-transition metal catalyst is excellent in separation and reusability from the reaction mixture, and thus is an organic synthesis means with a low environmental load, and is expected to be used in industry. However, the existing method for preparing organic polymer-supported phosphine is a copolymerization method using a ligand unit having a single polymerization reaction point, a monomer, and a cross-linking agent. The problem is that it acts as a steric hindrance to the center and is often less active than the corresponding homogeneous catalyst. In addition, the catalyst design utilizing the solid surface environment is difficult due to the flexibility of the flexible polymer chain.

  Under such circumstances, the present inventors have so far developed an organic polymer three-point crosslinked triarylphosphine (see the following formula) using a phosphine compound having three polymerization sites as a crosslinking agent. This organic polymer can spatially isolate metal coordination points, and based on this structure, it enables selective formation of metal-phosphorus 1: 1 type complexes to various transition metals. As a result, it has been found that a highly active coordination unsaturated complex is preferentially formed in a catalytic reaction system (Patent Document 1, Non-Patent Document 1).

Patent Document 1: WO2014 / 136909
Patent Document 2: CN10395386A
The entire description of Patent Literatures 1 and 2 is specifically incorporated herein by reference.

Non-Patent Document 1: Sawamura, M. et al. Angew. Chem. Int. Ed. 2013, 52, 12322
Non-Patent Document 2: Brunkan, NM; Gagne MR, J. Am. Chem. Soc. 2000, 122, 6217.
Non-Patent Document 3: Humphrey, SM et al. J. Am. Chem. Soc. 2013, 135, 16038.
All the descriptions of Non-Patent Documents 1 to 3 are specifically incorporated herein by reference.

  On the other hand, from the viewpoint of element strategy, development of a reaction using a first transition series metal such as cobalt or nickel that exists relatively abundantly on the earth as a catalyst has been demanded in recent years. Therefore, the present inventors examined the formation of a complex of a first transition series metal using the organic polymer three-point bridged triarylphosphine. As a result of investigation, the coordination power of the monodentate phosphine of the organic polymer three-point bridged triarylphosphine sometimes has room for improvement with respect to the first transition series metal.

  Therefore, the present invention provides an organic polymer capable of strong chelate coordination to various transition metal species including the first transition series metal, and an organic material including various transition metal species including the first transition series metal. An object is to provide a polymer complex, and further to provide a catalyst using these organic polymer complexes.

  The present inventors have made various studies to achieve the above object, and as a result, a polymer-supported bisphosphine obtained by using bisphosphine as an organic polymer four-point crosslinking agent and copolymerizing it with styrenes, Discovering that the present invention is capable of strong chelate coordination to various transition metal species including the first transition series metal and that the resulting complex exhibits excellent catalytic activity in various reactions. Completed.

  In addition, the following are mentioned as an example of the metal complex containing the similar organic polymer four point bridge | crosslinking bisphosphine. There is an organic polymer-supported bisphosphine-metal complex using a complex in which 1,2-bis [bis (4-styryl) phosphino] ethane is coordinated to a transition metal such as platinum or palladium as a four-point cross-linking agent. Reference 2). However, the polymer complex described in this document is formed by polymerizing a bisphosphine-containing monomer coordinated with a transition metal such as platinum. There is no description of an example in which a transition metal such as platinum in the polymer complex after polymerization is exchanged with another metal species. The reason for this is that, in polymerized four-point cross-linked bisphosphines, there are steric hindrances due to polymer chains, etc., so coordination to other metal species (metal exchange) is expected to be difficult. Can be mentioned. In addition, porous coordination polymers having palladium and platinum complexes with 1,2-bis (diphenylphosphino) benzene-type ligands introduced with carboxy groups as main constituents have been reported (Non-patented) Reference 3). In this document as well, the starting material (monomer) for polymerization is limited to bisphosphine-metal complexes prepared in advance. After building a porous coordination polymer, a metal species other than platinum is coordinated to the polymer complex. There is also no description (replacement of metal).

  Although it is not an example of a metal complex, there exists literature which discloses the monomer for manufacture of an organic polymer four-point bridged bisphosphine, and its homopolymerization (patent document 2). However, Patent Document 2 does not describe an example in which complexation to a transition metal and its immobilized metal complex are used for a catalytic reaction. Furthermore, it is different from the production method of the present invention in which a polymer is synthesized by copolymerization with a styrene monomer.

式（２）中、

は、無置換若しくは置換基を有する芳香族炭化水素基、又は無置換若しくは置換基を有する芳香族ヘテロ炭化水素基（但し、１〜３個のヘテロ原子を有し、ヘテロ原子は、窒素原子、酸素原子及び硫黄原子から選ばれる）であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、独立に、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴がそれぞれ結合するフェニレン基と共に形成する、直鎖又は架橋型ポリスチレン鎖であり、
前記架橋型ポリスチレン鎖は、式（３）で示されるビスホスフィン単位を少なくとも１つ含むことができ、

式（３）中、

は、式（２）と同義であり、
前記ポリスチレン鎖のフェニル基は無置換であるか、又は前記ポリスチレン鎖のフェニル基の少なくとも一部は置換基を有し、
Ｍは、配位子を有することができる遷移金属又は遷移金属イオンである。
[２]
前記遷移金属又は遷移金属イオンは、第一遷移元素（3d遷移元素）、第二遷移元素（4d遷移元素）及び第三遷移元素（5d遷移元素）から成る群から選ばれる少なくとも1種の金属又は金属イオンである、［１］に記載の錯体。
[３]
前記芳香族炭化水素基はアリール基であり、前記芳香族ヘテロ炭化水素基はヘテロアリール基である、［１］又は［２］に記載の錯体。
[４]
前記芳香族炭化水素基、前記芳香族ヘテロ炭化水素基、前記ポリスチレン鎖のフェニレン基が有する置換基は、炭素数１〜６のアルキル基である、［１］〜［３］のいずれか１項に記載の錯体。
[５]
一般式（３）で示されるビスホスフィン単位および前記Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴で示されるポリスチレン鎖中のスチレン単位の当量比は１：１０〜１０００の範囲である［１］〜［４］のいずれか１項に記載の錯体。
[６]
Ｍが有することができる配位子は、アルケン、ハロゲン、カルボニル、ヒドロキシ、ニトロ、アミノ、スルホニル、またはシアノである［１］〜［５］のいずれか１項に記載の錯体。
[７]
下記一般式（１）で示される高分子化合物と遷移金属Ｍを含有する化合物を混合して、下記式（２）で示される高分子遷移金属錯体を得る工程、を含む高分子遷移金属錯体の製造方法。

式（１）中、

は、無置換若しくは置換基を有する芳香族炭化水素基、又は無置換若しくは置換基を有する芳香族ヘテロ炭化水素基（但し、１〜３個のヘテロ原子を有し、ヘテロ原子は、窒素原子、酸素原子及び硫黄原子から選ばれる）であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は、独立に、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴がそれぞれ結合するフェニレン基と共に形成する、直鎖又は架橋型ポリスチレン鎖であり、
前記架橋型ポリスチレン鎖は、式（４）で示されるビスホスフィン単位を少なくとも１つ含むことができ、

式（４）中、

は、式（１）と同義であり、
前記ポリスチレン鎖のフェニル基は無置換であるか、又は前記ポリスチレン鎖のフェニル基の少なくとも一部は置換基を有する。

式中の

Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴の定義は、一般式（１）における定義と同じであり、但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴がそれぞれ結合するフェニレン基と共に形成する、ポリスチレン鎖が少なくとも１つ含むことができるビスホスフィン単位は、式（３）で示され、

式（３）中、

は、式（２）と同義であり、
Ｍは、配位子を有することができる遷移金属又は遷移金属イオンである。
[８]
前記芳香族炭化水素基はアリール基であり、前記芳香族ヘテロ炭化水素基はヘテロアリール基である［７］に記載の製造方法。
[９]
前記芳香族炭化水素基、前記芳香族ヘテロ炭化水素基、前記ポリスチレン鎖のフェニレン基が有する置換基は、炭素数１〜６のアルキル基である［７］又は［８］に記載の製造方法。
[１０]
遷移金属Ｍを含有する化合物は、Ｍが有することができる配位子を含み、前記配位子は、アルケン、ハロゲン、カルボニル、ヒドロキシ、ニトロ、アミノ、スルホニル、またはシアノである［７］〜［９］のいずれか１項に記載の製造方法。
[１１]
［１］〜［６］のいずれかに記載の高分子遷移金属錯体を含む有機化合物カップリング反応用触媒。
[１２]
前記有機化合物カップリング反応がＣ−Ｈ／Ｃ−Ｏカップリング反応である［１１］に記載の触媒。
[１３]
前記有機化合物カップリング反応がＣ−Ｎクロスカップリング反応である［１１］に記載の触媒。
[１４]
［１］〜［６］に記載の高分子遷移金属錯体を含むヒドロホウ素化反応用触媒。The present invention is as follows.
[1]
A polymer transition metal complex represented by the following general formula (2).

In formula (2),

Is an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted aromatic heterohydrocarbon group (provided having 1 to 3 heteroatoms, the heteroatoms being nitrogen atoms, Selected from an oxygen atom and a sulfur atom),
R ¹ , R ² , R ³ and R ⁴ are each a linear or cross-linked polystyrene chain formed independently with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are bonded,
The crosslinked polystyrene chain may include at least one bisphosphine unit represented by the formula (3),

In formula (3),

Is synonymous with formula (2),
The phenyl group of the polystyrene chain is unsubstituted, or at least a part of the phenyl group of the polystyrene chain has a substituent,
M is a transition metal or a transition metal ion that can have a ligand.
[2]
The transition metal or transition metal ion is at least one metal selected from the group consisting of a first transition element (3d transition element), a second transition element (4d transition element), and a third transition element (5d transition element) or The complex according to [1], which is a metal ion.
[3]
The complex according to [1] or [2], wherein the aromatic hydrocarbon group is an aryl group, and the aromatic heterohydrocarbon group is a heteroaryl group.
[4]
The aromatic hydrocarbon group, the aromatic heterohydrocarbon group, and the substituent that the phenylene group of the polystyrene chain has is an alkyl group having 1 to 6 carbon atoms, any one of [1] to [3] The complex described in 1.
[5]
The equivalent ratio of the bisphosphine unit represented by the general formula (3) and the styrene unit in the polystyrene chain represented by the R ¹ , R ² , R ³ and R ⁴ is in the range of 1:10 to 1000 [1] to The complex according to any one of [4].
[6]
The ligand according to any one of [1] to [5], wherein the ligand that M can have is alkene, halogen, carbonyl, hydroxy, nitro, amino, sulfonyl, or cyano.
[7]
A step of mixing a polymer compound represented by the following general formula (1) and a compound containing a transition metal M to obtain a polymer transition metal complex represented by the following formula (2): Production method.

In formula (1),

Is an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted aromatic heterohydrocarbon group (provided having 1 to 3 heteroatoms, the heteroatoms being nitrogen atoms, Selected from an oxygen atom and a sulfur atom),
R ¹ , R ² , R ³ and R ⁴ are each a linear or cross-linked polystyrene chain formed independently with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are bonded,
The crosslinked polystyrene chain may include at least one bisphosphine unit represented by the formula (4),

In formula (4),

Is synonymous with formula (1),
The phenyl group of the polystyrene chain is unsubstituted or at least a part of the phenyl group of the polystyrene chain has a substituent.

In the formula

The definitions of R ¹ , R ² , R ³ , and R ⁴ are the same as those defined in the general formula (1) except that R ¹ , R ² , R ³ , and R ⁴ are each formed with a phenylene group to which each is bonded. The bisphosphine unit that the polystyrene chain can contain at least one is represented by the formula (3):

In formula (3),

Is synonymous with formula (2),
M is a transition metal or a transition metal ion that can have a ligand.
[8]
The production method according to [7], wherein the aromatic hydrocarbon group is an aryl group, and the aromatic heterohydrocarbon group is a heteroaryl group.
[9]
The manufacturing method according to [7] or [8], wherein the substituent that the aromatic hydrocarbon group, the aromatic heterohydrocarbon group, and the phenylene group of the polystyrene chain have is an alkyl group having 1 to 6 carbon atoms.
[10]
The compound containing the transition metal M includes a ligand that M may have, and the ligand is an alkene, halogen, carbonyl, hydroxy, nitro, amino, sulfonyl, or cyano [7] to [ [9] The production method according to any one of [9].
[11]
[1] A catalyst for organic compound coupling reaction comprising the polymer transition metal complex according to any one of [6].
[12]
The catalyst according to [11], wherein the organic compound coupling reaction is a C—H / C—O coupling reaction.
[13]
The catalyst according to [11], wherein the organic compound coupling reaction is a CN cross-coupling reaction.
[14]
[1] A catalyst for hydroboration reaction comprising the polymer transition metal complex according to [6].

  According to the present invention, it is possible to provide an organic polymer four-point bridged bisphosphine capable of strong chelate coordination to various transition metal species including the first transition series metal. Using the four-point bridged bisphosphine, an organic polymer complex containing various transition metal species including the first transition series metal can be provided. Furthermore, a catalyst for coupling reaction using these organic polymer complexes can be provided.

3 shows ³¹ P CP / MAS NMR of [PdCl ₂ (3)]. FIG. 3 shows ³¹ P CP / MAS NMR of [Rh (3) (cod)] BF ₄ . FIG. ₃ shows ³¹ P NMR (CDCl ₃ ) of [Rh (dppbz) ₂ ] BF ₄ . The test result of the effect of the phosphorus content of a polystyrene four-point bridged bisphosphine is shown.

Ｍは、配位子を有することができる金属又は金属イオンである。A polymer transition metal complex represented by the following general formula (2).

M is a metal or metal ion that can have a ligand.

  The polymer transition metal complex is obtained by bonding a polymer compound represented by the following general formula (1) and M.

<High molecular compound represented by general formula (1)>

は、無置換若しくは置換基を有する芳香族炭化水素基、又は無置換若しくは置換基を有する芳香族ヘテロ炭化水素基である。但し、２つ存在するリン原子Ｐと結合する原子はそれぞれ炭素原子であり、かつ隣り合う炭素原子である。Where

Is an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted aromatic heterohydrocarbon group. However, the atom couple | bonded with two phosphorus atoms P which exist is a carbon atom, respectively, and is an adjacent carbon atom.

  As an aromatic hydrocarbon group, the aromatic hydrocarbon group which contains 6-14 carbon atoms and may be condensed is mentioned, for example. The monocyclic aromatic hydrocarbon group is, for example, a substituted or unsubstituted phenylene group. The polycyclic aromatic hydrocarbon group is, for example, a substituted or unsubstituted naphthalene group.

  Examples of the aromatic heterohydrocarbon group include 1 to 3 atoms selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom, and may be a condensed 5- to 14-membered aromatic heterohydrocarbon group. Is mentioned.

  Examples of the monocyclic aromatic heterohydrocarbon group include a substituted or unsubstituted azole group, oxol group, thiol group, pyridine group, pyrylium ion group, thiopyrylium ion group, azepine group, oxepin group, thiepine group, and imidazole. Groups, pyrazole groups, oxazole groups, thiazole groups, imidazoline groups, pyrazine groups, and thiazine groups.

  Examples of the polycyclic (fused) aromatic heterohydrocarbon group include a substituted or unsubstituted indole group, isoindole group, benzimidazole group, quinoline group, isoquinoline group, quinazoline group, phthalazine group, pteridine group, Examples thereof include a coumarin group, a chromone group, 1,4-benzodiazepine, a benzofuran group, an acridine group, a phenoxazine group, and a phenothiazine group.

  The substituent that the aromatic hydrocarbon group and the aromatic heterohydrocarbon group may have is not particularly limited, and examples thereof include a C1-6 alkyl group, a C1-6 perfluoroalkyl group, an alkoxy group, a siloxy group, A dialkylamino group etc. are mentioned. Examples of the C1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. Examples of the C1-6 perfluoroalkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, tridecafluorohexyl and the like. Examples of the siloxy group include trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldimethylsiloxy and the like. As an alkoxy group, a C1-6 alkoxy group is mentioned, for example. Examples of the C1-6 alkoxy group include a methoxy group, an ethoxy group, and a hexyloxy group. Examples of the dialkylamino group include dimethylamino and diethylamino. The substitution position of the substituent and the number of substituents are not particularly limited.

式（４）中の４つのフェニル基の任意の位置にそれぞれ結合する

は、ビニル基の重合反応により形成されるエチレン基である。R ¹ , R ² , R ³ and R ⁴ are independently a linear or cross-linked polystyrene chain formed together with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are bonded.
Each crosslinked polystyrene chain can contain at least one bisphosphine unit represented by the formula (4), and a crosslinked structure is formed by including the bisphosphine unit represented by the formula (4). The polystyrene chain containing no bisphosphine unit represented by the formula (4) is a linear polystyrene.

Bind to any position of the four phenyl groups in formula (4)

Is an ethylene group formed by a polymerization reaction of a vinyl group.

  The phenyl group of the polystyrene chain is unsubstituted unless it contains a repeating unit represented by formula (4), or at least a part of the phenyl group of the polystyrene chain has a substituent R. Examples of the substituent include a C1-6 alkyl group, a C1-6 alkoxy group, and a polar functional group. Examples of the C1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. Examples of the C1-6 alkoxy group include a methoxy group, an ethoxy group, and a hexyloxy group. Examples of the polar functional group include a hydroxyl group, a polyether group, an acetoxy group, an ester group, and an amide group. As a polyether group, the oligomer or polymer chain which has an ethylene glycol unit can be mentioned, for example, The number of ethylene glycol units can be 2 or more and 100 or less, for example. More specifically, the polyether group is, for example, a tetraethylene glycol monomethyl ether group. Examples of the ester group include an ester group with a lower alkyl group having 1 to 6 carbon atoms, and specific examples include a methyl ester group and an ethyl ester group. Examples of the substituent of the acyl group of the amide group include a lower alkyl group having 1 to 6 carbon atoms, and specific examples include a methylamide group and an ethylamide group. The substituent R having a high catalytic activity improving effect is, for example, a methyl group or a t-butyl group. The number of substituents that one phenyl group has is, for example, in the range of 1 to 5, preferably 1 to 3.

  The polymer compound represented by the general formula (1) is, for example, a copolymer obtained by copolymerizing a compound represented by the following general formula (5) with styrene or styrene having a substituent R. This copolymer is a copolymer represented by the general formula (1) and includes at least one bisphosphine unit represented by the general formula (4).

一般式（３）中の

は、一般式（１）と同義である。

In general formula (3)

Is synonymous with the general formula (1).

  By using the bisphosphine monomer of the above general formula (5) as the copolymerization monomer, it is introduced into the polystyrene chain. Since the bisphosphine monomer of the general formula (5) is tetrafunctional, each vinyl group is When introduced into different polystyrene chains, a copolymer in which one bisphosphine unit is contained as a copolymerized unit in four polystyrene chains can be obtained. Thereby, a styrene 4-point cross-linking phosphine unit is formed.

The amount of the bisphosphine unit introduced in the copolymer of the present invention is not particularly limited, but for example, the styrene unit can be in the range of 10 to 1000 in an equivalent ratio with respect to the bisphosphine unit 1. However, when the copolymer of the present invention is used as a ligand of the metal complex described later, the phosphorus of the bisphosphine unit becomes a site coordinated to the metal, and the resulting metal complex is used as a catalyst. Therefore, from the viewpoint that a relatively high catalytic activity per unit amount can be obtained, the amount of bisphosphine units is preferably relatively high. However, when the amount of the bisphosphine unit is excessive, the bisphosphine unit is too close and the copolymerization reaction is difficult to proceed due to steric hindrance, and the cross-linking ratio of the obtained copolymer is increased and the handling becomes difficult. there is a possibility. In view of such a viewpoint, the styrene unit of each polystyrene chain of R ¹ , R ² , R ³ , R ^{4 in} an equivalent ratio to the bisphosphine unit 1 is in the range of 1 to 200, preferably 5 to 150. And more preferably in the range of 10-100. In addition, the preferable range of the said equivalent ratio changes also with the kind of R of styrene which has the substituent R.

が無置換のフェニレン基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴が、独立に、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴がそれぞれ結合するフェニレン基と共に形成する、直鎖又は架橋型ポリスチレン鎖である場合、下記の模式的な化学式で示すことができる。式中、ＰＳは、直鎖のポリスチレン鎖であるか、又は式（４）で示されるビスホスフィン単位を含む架橋型のポリスチレン鎖であることができる。一般式（１）で示される高分子化合物は、遷移金属に対する配位子として機能し、配位子として用いることができる。Ｒは、置換基であるか、水素原子である。The polymer compound represented by the general formula (1) is:

Is an unsubstituted phenylene group, and R ¹ , R ² , R ³ and R ⁴ are independently formed with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are respectively bonded. In the case of a type polystyrene chain, it can be represented by the following schematic chemical formula. In the formula, PS can be a linear polystyrene chain or a crosslinked polystyrene chain containing a bisphosphine unit represented by formula (4). The polymer compound represented by the general formula (1) functions as a ligand for a transition metal and can be used as a ligand. R is a substituent or a hydrogen atom.

（２０）

(20)

が無置換のフェニレン基である一般式（１）で示される高分子化合物は、下記１で示される化合物をスチレン及び／又は置換基を有するスチレンと共重合することが得られる。下記１で示される化合物は、詳細は実施例に記載するが、ｐ−ブロモスチレンと1,2-ビス(ジクロロホスフィノ)ベンゼンを原料として合成することができる。

が置換のフェニレン基である場合、あるいは、フェニレン基以外の場合にも同様の方法で、一般式（１）で示される高分子化合物の原料モノマーを合成することができる。1,2-ビス(ジクロロホスフィノ)ベンゼンのベンゼンを別の芳香族炭化水素基又はヘテロ芳香族炭化水素基に替えることで、前記一般式（３）で示される種々のビスホスフィンスチレンモノマーを調製できる。

The polymer compound represented by the general formula (1) in which is an unsubstituted phenylene group can be obtained by copolymerizing the compound represented by the following 1 with styrene and / or styrene having a substituent. Although the compound shown by 1 below is described in detail in the Examples, it can be synthesized using p-bromostyrene and 1,2-bis (dichlorophosphino) benzene as raw materials.

In the case where is a substituted phenylene group or other than the phenylene group, the raw material monomer of the polymer compound represented by the general formula (1) can be synthesized by the same method. Various bisphosphine styrene monomers represented by the above general formula (3) are prepared by replacing benzene of 1,2-bis (dichlorophosphino) benzene with another aromatic hydrocarbon group or heteroaromatic hydrocarbon group. it can.

  In the formula (20), the polystyrene unit chain PS in the copolymerization component is described independently, but each polystyrene unit chain PS can be an independent chain even in a portion where the chain is omitted. It may be linked to other polystyrene unit chains PS shown in FIG.

  In the polystyrene unit chain PS in the copolymer of the above formula (20), when R is a hydrogen atom, the portion other than the bisphosphine unit is a styrene unit. When R is other than a hydrogen atom, each styrene unit of the polystyrene chain PS has R as a substituent. Alternatively, each styrene unit of the polystyrene chain PS has at least two of R as a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, and a polar functional group. You can also. The different R sequences in that case can be random. Furthermore, the introduction of bisphosphine units into the polystyrene unit chain PS is random. Therefore, the copolymer of the present invention is a random copolymer.

  In the copolymer of the present invention, by introducing a residue other than a hydrogen atom as a substituent R on the phenyl ring of the styrene unit, when a complex with a transition metal using this copolymer is used as a catalyst, The catalytic activity can also be improved. In the example of R, as described above, the lower alkyl group having 1 to 6 carbon atoms is a lower alkoxy group having 1 to 6 carbon atoms and a polar functional group. The substituent R having a high catalytic activity improving effect is, for example, a methyl group or a t-butyl group.

  The plurality of polystyrene chains in the copolymer of the present invention can include crosslinking by divinylbenzene units. By introducing a cross-link by divinylbenzene units into the copolymer of the present invention, the strength of the copolymer can be adjusted and the moldability can also be improved. However, since the bisphosphine unit also has a function of crosslinking the polystyrene chain, it does not include crosslinking by the divinylbenzene unit, and the copolymer strength can be adjusted and the moldability can be improved only by introducing the bisphosphine unit. In consideration of the amount of bisphosphine units introduced and the desired copolymer strength and moldability, the amount of divinylbenzene units introduced can be determined as appropriate.

  The amount of crosslinking by the divinylbenzene unit can be appropriately determined in consideration of the quantitative ratio between the styrene unit and the bisphosphine unit. For example, when 60 equivalents of styrene units are copolymerized with respect to 1 equivalent of bisphosphine units shown in the examples, and divinylbenzene units are further copolymerized, the equivalent ratio of divinylbenzene units is, for example, 0 In the range of 1 to 5 and may be in the range of 0.2 to 4. As described above, if the amount of divinylbenzene units introduced is increased, the strength of the copolymer can be increased or the moldability can be improved.

  In the case of a copolymer containing divinylbenzene units, more generally, the equivalent ratio of bisphosphine units, styrene units and divinylbenzene units is, for example, in the range of 1:10 to 1000: 0.1 to 20. Can do. The range is preferably 1:20 to 200: 0.1 to 10, more preferably 1:30 to 200: 0.1 to 10, still more preferably 1:40 to 200: 0.1 to 10. The divinylbenzene can be, for example, m-divinylbenzene, p-divinylbenzene, or a mixture thereof. Furthermore, divinylbenzene may contain ethyl vinylbenzene as an impurity for manufacturing reasons, and the one containing this impurity as divinylbenzene can also be used. In addition to the divinylbenzene unit, it may contain an ethylvinylbenzene unit.

  Since the polymer compound (copolymer) represented by the general formula (1) is a crosslinked polymer compound (copolymer), it is technically difficult to specify the molecular weight. Instead of molecular weight or degree of polymerization, the swelling volume in organic solvent is displayed. The polymer compound (copolymer) represented by the general formula (1) is, for example, hexane, dichloromethane, toluene, t-butyl methyl ether, tetrahydrofuran, cyclopentyl methyl ether, diethyl ether, acetone, ethyl acetate, The swelling volume in dimethylformamide and methanol is in the range of 2.0 to 7.0 mL / g. Preferably it is the range of 3.0-7.0 mL / g. Particularly preferably, the swelling volume in toluene or cyclopentyl methyl ether is in the range of 2.0 to 7.0 mL / g, more preferably in the range of 3.0 to 7.0 mL / g.

  The copolymer of the present invention comprises a random copolymerization of a bisphosphine styrene monomer represented by the general formula (3), styrene and / or a styrene having a substituent R, and a bisphosphine styrene monomer represented by the general formula (3). , Styrene and / or styrene having a substituent R and divinylbenzene can be synthesized by random copolymerization. The bisphosphine styrene monomer (compound 1) represented by the general formula (3) is a compound reported in Patent Document 1. However, this document does not describe spectral data. In the Examples, Synthesis Example is shown as Compound 1. Styrene and divinylbenzene containing R are commercially available. The substituent R of the styrene having the substituent R is the same as that described in the styrene unit having the substituent R, and R is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A lower alkoxy group or a polar functional group. By using at least two types of styrene having different substituents R, a copolymer containing styrene units having two types of substituents R can be obtained.

  The copolymer can be synthesized by, for example, suspension polymerization of the above two to four types of monomers at a predetermined ratio using a known polymerization initiator. The suspension polymerization can be performed, for example, at 50 to 100 ° C. for 1 to 72 hours. However, it is not intended to be limited to this range, and can be appropriately determined according to the type and ratio of the monomer used as the raw material, the type and amount of the polymerization initiator used, the conditions for suspension polymerization, and the like.

<Complex>
The complex of the present invention is a polymer transition metal complex represented by the following general formula (2), and includes a polymer compound (copolymer) represented by the above general formula (1) and a transition metal M.

  Examples of the transition metal include a first transition element (3d transition element), a second transition element (4d transition element), and a third transition element (5d transition element). As the first transition element, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu ) And zinc (Zn). Second transition elements include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag ) And cadmium (Cd). Examples of the third transition element (5d transition element) include tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and lead (Pb). From the viewpoint of catalytic activity, transition metals are, for example, palladium (Pd), iridium (Ir), rhodium (Rh), platinum (Pt), ruthenium (Ru), cobalt (Co), nickel (Ni), copper ( Cu) or the like is preferable. However, it is not intended to be limited to these elements. The complex of the present invention contains the copolymer of the present invention as a ligand.

式（３）中、

は、式（２）と同義であり、４つのフェニル基の任意の位置にそれぞれ結合する

は、ビニル基の重合反応により形成されるエチレン基である。In the complex of the present invention, the copolymer represented by the general formula (2) includes a bisphosphine unit represented by the general formula (3), and includes two phosphorus (P ) Coordinates to the transition metal. Therefore, even when the transition metal is the first transition element (3d transition element), a stable complex can be formed.

In formula (3),

Is synonymous with formula (2), and is bonded to any position of the four phenyl groups.

Is an ethylene group formed by a polymerization reaction of a vinyl group.

  The complex of the present invention includes, for example, alkenes (for example, aliphatic alkenes and alicyclic alkenes (cycloalkenes), which are widely used as ligands for transition metal complexes. Examples of aliphatic alkenes: ethylene, Examples of alicyclic alkenes: 1,5-cyclooctadiene), halogen (fluorine, chlorine, bromine, iodine), carbonyl (ester, aldehyde, ketone, amide), hydroxy, nitro, amino, sulfonyl, cyano, etc. Groups can further be included. The type and number of these ligands (the number of ligands to one transition metal) are appropriately determined according to the type of transition metal. The complex of the present invention is obtained by mixing a complex composed of a transition metal and one or more of the above ligands and a polymer compound (copolymer) represented by the general formula (1) in an organic solvent. Can be prepared. The organic solvent to be used can be appropriately selected from, for example, toluene used in the examples and an organic solvent for measuring the swelling volume of the polymer compound (copolymer) of the present invention.

  In the complex of the present invention, the equivalent ratio of the bisphosphine unit and the transition metal in the polymer compound (copolymer) of the present invention is 1: 1. That is, one bisphosphine unit (including two phosphorus) per metal forms a complex. In the complex of the present invention, a metal complex is formed in at least a part of the bisphosphine unit in the polymer compound (copolymer). From the viewpoint that the complex of the present invention is used in the catalyst described later and the catalytic reaction activity per unit mass is high, it is represented by the general formula (3) in the polymer compound (copolymer) forming the metal complex. The more bisphosphine units, the better. For example, 50 to 100%, preferably 70 to 100%, more preferably 90 to 100% of bisphosphine units in the copolymer form a metal complex.

<Catalyst>
The present invention relates to a coupling reaction catalyst containing the complex of the present invention. The coupling reaction means a reaction in which a new bond is generated between carbon of an organic compound and carbon of the organic compound, or between carbon of the organic compound and a hetero atom of the organic compound. Examples of the coupling reaction include a C—C coupling reaction, a C—N coupling reaction, a C—H / C—O coupling reaction, and the like.

  Representative couplings include Suzuki-Miyaura coupling, and preferably a diaryl derivative, an alkenyl aryl derivative or 1 by a condensation reaction of an aryl halide or alkenyl halide with an aryl boron derivative or alkenyl boron derivative. , 3-dienes. As a specific example, for example, a reaction in which a halogenated benzene and phenylboronic acid are condensed to form biphenyl can be mentioned.

  Examples of the halogen of the organic halide include a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group of the halogenated aryl include a carbocyclic aromatic group and a heterocyclic aromatic group. Examples of the carbocyclic aromatic group include monocyclic, polycyclic or condensed cyclic carbocyclic aromatic groups having 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms and 6 to 12 carbon atoms. It is done. Examples of such carbocyclic aromatic groups include a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthryl group. Moreover, as a heterocyclic aromatic group, 1 to 4, preferably 1 to 3 or 3 to 8 members containing a hetero atom consisting of a nitrogen atom, an oxygen atom or a sulfur atom, Preferably, a monocyclic, polycyclic, or condensed heterocyclic group having a 5- to 8-membered ring is used. Examples of such a heterocyclic group include a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, an indole group, and a benzoimidazolyl group. These aryl groups may further have a substituent, and such a substituent is not particularly limited as long as it does not adversely affect the reaction. For example, the above-described halogen atom, nitro group, substituted or An unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms, Examples include 1 to 10 alkoxycarbonyl groups. The alkenyl group of the halogenated alkenyl is a substituted or unsubstituted vinyl group, and the substituent of the vinyl group is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, A substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, a substituted or unsubstituted carbon number 7 to 20 carbon atoms, Preferably 7-12 alkynyl groups etc. are mentioned. These substituents are not particularly limited as long as they do not adversely influence the reaction.

  Examples of the boron derivative include mono-, di- or triesters of orthoboric acid or derivatives thereof, but are not necessarily limited to orthoboric acid or derivatives thereof. Examples of the aryl group of the aryl boron derivative include aromatic rings such as a substituted or unsubstituted phenyl group, naphthyl group, pyridine group, and furyl group, and these substituents are particularly those that do not adversely affect the reaction. Without limitation, for example, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, a substituted or unsubstituted C 1-20, preferably a 1-10 alkyl group, a substituted or unsubstituted C 1-20, preferably Includes 1 to 10 alkoxy groups. Examples of the alkenyl group of the alkenyl boron derivative include a substituted or unsubstituted vinyl group, and these substituents are not particularly limited as long as they do not adversely influence the reaction.

  An example of the coupling reaction is the Mizorogi-Heck reaction. This reaction is a reaction for producing an aryl alkene or 1,3-diene by a condensation reaction between an alkene and an aryl halide or alkenyl halide.

  Examples of the alkenes include ethylene derivatives having at least one hydrogen atom. Preferred are ethylene derivatives in which at least one hydrogen atom of ethylene is substituted with a keto group, a substituted or unsubstituted alkoxycarbonyl group, and / or a substituted or unsubstituted aryl group. Examples of the aryl group include the carbocyclic aromatic group and the heterocyclic aromatic group described above. These substituents are not particularly limited as long as they do not adversely influence the reaction, and examples thereof include the above-described substituents. More preferable alkenes include substituted or unsubstituted 3-ketoalkenes, substituted or unsubstituted styrene derivatives, substituted or unsubstituted (meth) acrylic acid esters, and the like. Examples of the ester residue of the acrylate esters include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and these substituents are particularly limited as long as they do not adversely affect the reaction. There is no. Examples of preferable alkenes include, for example, acrylic acid esters such as methyl acrylate, 3-ketoalkenes such as 3-ketobutene, and styrene derivatives such as styrene, but are not limited to these compounds. .

  Examples of the halogen of the organic halide include a chlorine atom, a bromine atom, and an iodine atom. The aryl or alkenyl group may be an aliphatic or aromatic substituent, and examples thereof include a substituted or unsubstituted vinyl group and a substituted or unsubstituted aryl group. The aryl group includes the carbocyclic aromatic group described above. And aromatic aromatic groups. These substituents are not particularly limited as long as they do not adversely influence the reaction.

  As an example of the coupling reaction, Stille coupling can also be mentioned. Specific examples include biaryls, arylalkenes, or 1,3-dienes by a condensation reaction between an aryl or alkenyl tin compound and an aryl halide or alkenyl halide.

  Examples of the substituent that the tin compound has include an aryl group, for example, an aromatic ring such as a substituted or unsubstituted phenyl group, naphthyl group, pyridine group, and furyl group, and these substituents have an adverse effect on the reaction. For example, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, a substituted or unsubstituted alkyl group having 1 to 20, preferably 1 to 10, carbon atoms, substituted or unsubstituted And an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Further, tin compounds having an alkenyl group may be used, and examples of the alkenyl group include substituted or unsubstituted vinyl groups, and these substituents are not particularly limited as long as they do not adversely influence the reaction.

  An example of the coupling reaction is Sonogami coupling. Specifically, the reaction which produces | generates aryl alkyne or alkenyl alkyne by condensation reaction with alkyne and aryl halide or alkenyl halide can be mentioned.

  Examples of the substituent of the alkynes include a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, furyl group and the like, and these substituents are not limited if they do not adversely affect the reaction. There is no restriction | limiting in particular, For example, halogen atoms, such as a chlorine atom, a bromine atom, or an iodine atom, a substituted or unsubstituted C1-C20, Preferably a C1-C10 alkyl group, a substituted or unsubstituted C1-C20 , Preferably 1-10 alkoxy groups etc. are mentioned. Moreover, as a substituent of alkynes, a substituted or unsubstituted vinyl group is mentioned, There is no restriction | limiting in particular as long as these substituents do not have a bad influence on reaction.

  Examples of the halogen of the organic halide include a chlorine atom, a bromine atom, and an iodine atom. The aryl group or alkenyl group may be an aliphatic or aromatic substituent, and examples thereof include a substituted or unsubstituted vinyl group and a substituted or unsubstituted aryl group. The aryl group includes the carbocyclic group described above. Aromatic and heterocyclic aromatic groups are exemplified. These substituents are not particularly limited as long as they do not adversely influence the reaction.

  Examples of the coupling reaction include Buchwald-Hartwig coupling. Specifically, for example, amines having one or more alkyl groups or aryl groups and aryl halides or alkenyl halides using a carbon-oxygen or carbon-sulfur, more preferably carbon-nitrogen bond-forming reaction, This is a production reaction of substituted amines by the condensation reaction of

  As the substituent of the amines, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, pyridyl group, furyl group, or the like. These substituents are not particularly limited as long as they do not adversely affect the reaction. For example, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, a substituted or unsubstituted carbon number of 1 -20, preferably 1-10 alkyl groups, substituted or unsubstituted C1-C20, preferably 1-10 alkoxy groups.

  Examples of the halogen of the organic halide include a chlorine atom, a bromine atom, and an iodine atom. The aryl group or alkenyl group may be an aliphatic or aromatic substituent, and examples thereof include a substituted or unsubstituted vinyl group and a substituted or unsubstituted aryl group. The aryl group includes the carbocyclic group described above. Aromatic and heterocyclic aromatic groups are exemplified. These substituents are not particularly limited as long as they do not adversely influence the reaction.

  In the coupling reaction using the catalyst of the present invention, the reaction conditions (solvent, temperature, time, etc.) can be appropriately determined according to the type of raw material. The reaction temperature can be appropriately selected within a range from room temperature to the boiling point of the solvent, for example.

  Hereinafter, the present invention will be described in more detail based on examples. However, the examples are illustrative of the present invention, and the present invention is not intended to be limited to the examples.

The reaction vessel was heated, vacuum-cooled and dried, and the reaction was carried out in an argon or nitrogen atmosphere. Stirring of the reaction solution was performed using a magnetic stirrer coated with Teflon (registered trademark). Bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ ) was purchased from Kanto Chemical Co. and recrystallized from toluene / 1,5-cyclooctadiene. Cobalt iodide (99.999%) was purchased from Aldrich, 1,2-bis (dichlorophosphino) benzene from Wako Pure Chemical Industries, and 4-bromostyrene from Tokyo Chemical Industry. Pinacol borane was purchased from Tokyo Chemical Industry and purified by vacuum distillation. Styrene, 4- (t-butyl) styrene and divinylbenzene were purchased from Tokyo Chemical Industry and purified through an activated alumina column. The solvent used was a Kanto Chemical dehydration grade, which was further degassed by the coagulation-melting method and dehydrated using molecular sieve 4A. JEOL ECX-400 ( ¹ H; 399.8 MHz, ¹³ C; 100.5 MHz, ³¹ P; 161.8 MHz) was used for NMR measurement (liquid). Bruker MSL-300 ( ¹³ C; 75.5 MHz, ³¹ P; 121.5 MHz) was used for CP / MAS NMR measurement (solid). Various NMR chemical shifts were referred to tetramethylsilane ( ¹ H; 0 ppm), deuterated chloroform ( ¹³ C; 77.0 ppm), and 85% phosphoric acid ( ³¹ P; 0 ppm).

Synthesis of 1,2-bis [bis (4-styryl) phosphino] benzene (compound 1)

Compound 1 is reported in Patent Document 2. However, spectral data is not described.
A magnetic stirring bar was placed in a 300 mL two-necked eggplant type flask, and tetrahydrofuran (72 mL) and 4-bromostyrene (2.6 g, 14.4 mmol) were sequentially added under an argon atmosphere. After cooling the reaction solution to -78 ° C, n-butyllithium (8.5 mL, 1.6 M hexane solution, 13.6 mmol) was added dropwise and stirred at -78 ° C for 2 hours to prepare the corresponding organolithium reagent. Further, 1,2-bis (dichlorophosphino) benzene (0.84 g, 3.0 mmol) was added at −78 ° C., and the mixture was gradually warmed to room temperature and stirred for 4 hours. After adding methanol to the reaction mixture, the organic solvent was distilled off under reduced pressure. This crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 97: 3) to isolate Compound 1. Yield 0.98 g, Yield 59%

1 compound data:
Mp: 69-71 ℃
¹ H NMR (CDCl ₃ ): δ 5.23 (d, J = 11.2 Hz, 4H), 5.72 (d, J = 18.0 Hz, 4H), 6.64 (dd, J = 11.2, 18.0 Hz, 4H), 7.08-7.13 (m, 10H), 7.19-7.27 (m, 10H).
¹³ C NMR (CDCl ₃ ): δ 114.42, 126.07 (t, J = 3 Hz), 129.08, 133.50-134.35 (m), 136.34, 136.44, 137.59, 143.57 (t, J = 10 Hz).
³¹ P NMR (CDCl ₃ ): δ-14.4.
HRMS-EI (m / z): [M] ⁺ calcd for C ₃₈ H ₃₂ P ₂ , 550.19792; found, 550.19617.

Synthesis of polystyrene four-point bisphosphine (2)

  Put a stir bar in a 300 mL three-necked eggplant-shaped flask and add sodium chloride (3 g), acacia gum (2.4 g), and water (60 mL; argon bubbling) sequentially in an argon atmosphere to obtain a homogeneous solution. Further, argon gas was bubbled for 60 minutes. To this solution is chlorobenzene of 1,2-bis [bis (4-styryl) phosphino] benzene (1 eq, 0.25 mmol), styrene (60 eq, 15 mmol) and azobisisobutyronitrile (1.2 eq, 0.3 mmol) The solution (3 mL) was added, and the mixture was stirred for 18 hours while heating to 75 ° C. to carry out suspension polymerization. After cooling the reaction product to room temperature, the insoluble material is collected by filtration, washed successively with water, methanol, toluene-methanol mixed solvent, tetrahydrofuran and methanol, and then dried in vacuo at 100 ° C. Polystyrene four-point crosslinked bisphosphine (2) Obtained as a white bead solid (1.07 g, 63 wt%). The obtained polymer beads were sieved, and those having a particle size of 250-710 μm were used for the catalytic reaction.

Since the polymer obtained by this reaction is an insoluble solid, it is difficult to precisely determine the detailed molecular weight and degree of polymerization. The composition ratio of the polymer was calculated to be equal to the charging ratio assuming that the respective reactants were polymerized with the same reactivity (estimated bisphosphine content [PP] 0.15 mmol / g). In addition, from the result of ¹³ C CP / MAS NMR measurement of the product, the peak derived from the vinyl group of compound 1 (around 115 ppm) was not observed, indicating that the title four-point bridged bisphosphine 2 was produced. To be judged.
Compound data for polystyrene 4-point bridged bisphosphine 2:
³¹ P CP / MAS NMR: δ -17.
¹³ C CP / MAS NMR: δ 33-60 (br), 130, 148.

Synthesis of polystyrene four-point bisphosphine (3)

  Put a stir bar in a 300 mL three-necked eggplant-shaped flask and add sodium chloride (3 g), acacia gum (2.4 g), and water (60 mL; argon bubbling) sequentially in an argon atmosphere to obtain a homogeneous solution. Further, argon gas was bubbled for 60 minutes. To this solution was added 1,2-bis [bis (4-styryl) phosphino] benzene (1 eq, 0.25 mmol), 4- (t-butyl) styrene (60 eq, 15 mmol) and azobisisobutyronitrile (1.2 Equivalent, 0.3 mmol) of a chlorobenzene solution (3 mL) was added, and the mixture was stirred for 18 hours while heating to 75 ° C. to carry out suspension polymerization. After cooling the reaction product to room temperature, the insoluble material is collected by filtration, washed successively with water, methanol, toluene-methanol mixed solvent, tetrahydrofuran and methanol, and then dried in vacuo at 100 ° C. Polystyrene four-point crosslinked bisphosphine (3) Obtained as a white bead solid (2.3 g, 90 wt%). The obtained polymer beads were sieved, and those having a particle size of 250-710 μm were used for the catalytic reaction.

Since the polymer obtained by this reaction is an insoluble solid, it is difficult to precisely determine the detailed molecular weight and degree of polymerization. The composition ratio of the polymer was calculated to be equal to the charging ratio assuming that the polymerization of each reactant was progressed with the same reactivity (estimated bisphosphine content [PP] 0.10 mmol / g). In addition, from the result of ¹³ C CP / MAS NMR measurement of the product, the peak derived from the vinyl group of compound 1 (around 115 ppm) was not observed, indicating that the title four-point bridged bisphosphine 3 was produced. To be judged.

Compound data for polystyrene four-point bisphosphine 3:
³¹ P CP / MAS NMR: δ -17.
¹³ C CP / MAS NMR: δ 34, 36, 37-59 (br), 120-139 (br), 145, 150.

  Polystyrene four-point cross-linked bisphosphine 3 ([PP] 0.05-0.57 mmol / g) with different bisphosphine content is 1,2-bis [bis (4-styryl) phosphino] benzene and 4- (t-butyl) styrene These were synthesized by changing the charging ratio of each as shown in Table 1 (1: 120-1: 7.5). In addition, an organic polymer 4 ([P-P] 1.8 mmol / g) obtained by homopolymerization of 1,2-bis [bis (4-styryl) phosphino] benzene was synthesized.

Evaluation of swelling characteristics of polystyrene four-point bisphosphine:
100 mg of polystyrene four-point cross-linked bisphosphine (particle size 250-500 μm) was placed in a 1.0 mL syringe with a filter paper and graduated, and 1.0 mL of a suitable organic solvent was added and allowed to stand for 15 minutes. Tables 2 and 3 show the results of measuring the volume of the swollen polymer after removing excess solvent.

PdCl ₂ (cod) and 3 complexation experiment:

A stirrer, polystyrene four-point cross-linked phosphine 3 (0.2 g, [PP] 0.10 mmol / g), PdCl ₂ (cod) (11.3 mg, 0.04 mmol) and tetrahydrofuran (4 mL) were placed in a 10 mL screw test tube. The mixture was further stirred at room temperature for 1 hour. The reaction product was collected by filtration, washed with dichloromethane, and then dried in vacuo at 60 ° C. to obtain [PdCl ₂ (3)] (0.2 g). After distilling off the organic solvent of the filtrate under reduced pressure, unreacted PdCl ₂ (cod) (7.0 mg) was recovered. Assuming 3 bisphosphine moieties were reacted 1: 1 with palladium, the bisphosphine content was estimated to be 0.07 mmol / g. In the examples of the catalytic reactions described below, the amount of substance was calculated using the estimated bisphosphine content calculated from the charge ratio of raw material monomers in polymer synthesis (see Tables 4 to 7).

Compound data for [PdCl ₂ (3)] (see Figure 1):
³¹ P CP / MAS NMR: δ 60.
¹³ C CP / MAS NMR: δ 34, 36, 38-60 (br), 117-137 (br), 145, 149.
^{The 31} P CP / MAS NMR measurement signal (60 ppm) is the ³¹ P NMR signal (63.8 ppm for a known compound PdCl ₂ (dppbz) (dppbz = 1,2- (diphenylphosphino) benzene) with a similar structure: McFarlane, HCE; McFarlane, W. Polyhedron 1999, 18, 2117.), which is almost the same as that of the title compound PdCl ₂ (3).

Rh [cod] ₂ BF ₄ and 3 complexation experiment (Rh / 3 1: 2):

In a 5 mL screw test tube, stir bar, polystyrene four-point phosphine 3 (0.2 g, [PP] 0.10 mmol / g, 0.02 mmol), [Rh (cod) ₂ ] BF ₄ (0.01 mmol) and dichloromethane ( 2 mL) was added, and the mixture was stirred at room temperature for 2 hours. The reaction product was collected by filtration, washed with dichloromethane and diethyl ether, and the obtained solid was dried in vacuo. ³¹ P CP / MAS NMR measurement of this product (FIG. 2) confirmed the formation of [Rh (3) (cod)] BF ₄ (53 ppm) in addition to unreacted bisphosphine 3 (-17 ppm).

^{The 31} P CP / MAS NMR measurement signal (53 ppm) is almost identical to the ³¹ P NMR signal (58.0 ppm) of the compound [Rh (dppbz) (cod)] BF ₄ having a similar structure. It is judged that the compound [Rh (3) (cod)] BF ₄ was produced.

Compound data for [Rh (dppbz) (cod)] BF ₄ :
Mp: 175 ° C (decomp.).
¹ H NMR (CDCl ₃ ): δ 2.30-2.50 (m, 8H), 5.08 (br-s, 4H), 7.47-7.58 (m, 20H), 7.58-7.61 (m, 4H).
¹³ C NMR (CDCl ₃ ): δ 29.95, 103.15, 129.48-129.80 (m), 129.95-130.80 (m), 131.82, 132.50-132.95 (m), 133.13, 141.40-142.45 (m).
³¹ P NMR (CDCl ₃ ): δ 58.0 (d, J _P-Rh = 152 Hz).
HRMS-ESI (m / z) Calcd for [M-BF ₄ ] ⁺ C ₃₈ H ₃₆ P ₂ Rh, 657.13473; found 657.13495.

Rh [cod] ₂ BF ₄ and dppbz complexation experiment (Rh / dppbz 1: 2):

A stirrer, dppbz (0.02 mmol), [Rh (cod) ₂ ] BF ₄ (0.01 mmol) and deuterated chloroform (1 mL) were added to a 5 mL screw mouth test tube, and the mixture was stirred at room temperature for 10 minutes. ³¹ P NMR measurement of this product (FIG. 3) confirmed the production of [Rh (dppbz) ₂ ] BF ₄ (62.7 ppm). In this case, unreacted dppbz (-13.8 ppm; Kyba, EP; Kerby, MC; Rines, SP Organometallics 1986, 5, 1189.) and [Rh (dppbz) (cod)] BF ₄ (-58.0 ppm) Was not observed. The above results indicate that polystyrene four-point cross-linking phosphine is effective in controlling the coordination number of transition metals.

Compound data for [Rh (dppbz) ₂ ] BF ₄ :
Mp:> 200 ° C.
¹ H NMR (CDCl ₃ ): δ 6.80-6.90 (m, 16H), 7.07-7.12 (m, 16H), 7.37-7.42 (m, 16H).
¹³ C NMR (CDCl ₃ ): δ 128.68, 130.77, 131.45-132.05 (m), 132.93, 142.70-144.10 (m).
³¹ P NMR (CDCl ₃ ): δ 62.9 (d, J _P-Rh = 134 Hz).
HRMS-ESI (m / z) Calcd for [M-BF ₄ ] ⁺ C ₆₀ H ₄₈ P ₄ Rh, 995.17615; found 995.17544.

Nickel-catalyzed CH / CO coupling reaction between azoles and phenol derivatives:
In the cross-coupling reaction, generally, a reaction that forms a carbon-carbon (heteroelement) bond in the presence of a noble metal catalyst such as palladium using an organometallic reactant as a nucleophile and a halide as an electrophile. Widely used. In 2012, Itami et al. Reported that the CH / CO coupling reaction between azoles and phenol derivatives proceeded in the presence of a nickel catalyst to yield (hetero) biaryls (references; Itami, K. et. al. J. Am. Chem. Soc. 2012, 134, 169.). In this reaction, electron-rich and sterically bulky 1,2-bis (dicyclohexylphosphino) ethane ligand is specifically effective, promoting the oxidative addition of CO bond to nickel and the oxidative addition complex (Reference: Yamaguchi, J .; Lei, A .; Itami, K. et al. J. Am. Chem. Soc. 2013, 135, 16384.). The inventor of the present invention has reported that a polystyrene four-point crosslinked bis having 1,2-bis (diphenylphosphino) benzene as a basic skeleton, which has poor electron donating ability and steric bulk compared to 1,2-bis (dicyclohexylphosphino) ethane. We have found that phosphine is effective in this nickel-catalyzed CH / CO coupling reaction. In the inventors' prior invention, polystyrene three-point bridged triarylphosphine 5 (Patent Document 1, Non-Patent Document 1) and 1,2-bis (diphenylphosphino) benzene (Non-Patent Document 3), the reaction is almost From the fact that it does not proceed, the catalytic activity is clearly improved by immobilizing the bisphosphine ligand.

Under nitrogen atmosphere, in a 10 mL screw-cap test tube, a magnetic stir bar, ligand (0.006 mmol) and bis (1,5-cyclooctadiene) nickel (0.005 mmol) in 1,4-dioxane (0.5 mL) And stirred at room temperature for 10 minutes. Subsequently, benzoxazole (0.1 mmol), 2-naphthyl vibalate (0.15 mmol), cesium carbonate (0.2 mmol), and 1,4-dioxane (0.5 mL) were added in that order, and a Teflon (registered trademark) cap with packing was used. The test tube was closed and stirred for 24 hours while heating to 120 ° C. The yield of the desired coupling product 2- (2-naphthyl) benzoxazole was calculated by ¹ H NMR measurement using 1,1,2,2-tetrachloroethane as an internal standard. The results of the ligand effect are shown in Table 4. Furthermore, the crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 95: 5), and the coupling product was isolated. Experiment number 21: Yield 19.2 mg, Yield 78%

Compound data for 2- (2-naphthyl) benzoxazole:
¹ H NMR (CDCl ₃ ): δ 7.35-7.40 (m, 2H), 7.55-7.60 (m, 2H), 7.60-7.65 (m, 1H), 7.78-7.83 (m, 1H), 7.87-7.92 (m , 1H), 7.96-8.01 (m, 2H), 8.32 (dd, J = 1.6 Hz, 8.4 Hz 1H), 8.79 (s, 1H).
¹³ C NMR (CDCl ₃ ): δ 110.58, 120.01, 123.94, 124.38, 124.63, 125.16, 126.89, 127.78, 127.90, 128.12, 128.76, 128.94, 132.95, 134.72, 142.21, 150.85, 163.18.

反応条件：ベンゾオキサゾール（0.1 mmol）、ビバル酸 2-ナフチル（0.15 mmol）、Ni(cod)₂ (0.005 mmol, 5 mol%)、配位子（0.006 mmol, 6 mol%）、炭酸セシウム（0.2 mmol）、1,4-ジオキサン（1 mL）、24時間。括弧内は単離収率。

Reaction conditions: benzoxazole (0.1 mmol), 2-naphthyl vivalate (0.15 mmol), Ni (cod) ₂ (0.005 mmol, 5 mol%), ligand (0.006 mmol, 6 mol%), cesium carbonate (0.2 mmol), 1,4-dioxane (1 mL), 24 hours. The isolated yield is in parentheses.

Effect of phosphorus atom content on polystyrene four-point bisphosphine:
Under a nitrogen atmosphere, add a magnetic stir bar, ligand (0.006 mmol) and bis (1,5-cyclooctadiene) nickel (Ni (cod) ₂ ) (0.005 mmol) -A dioxane solution (0.5 mL) was added, and the mixture was stirred at room temperature for 10 minutes. Subsequently, benzoxazole (0.1 mmol), 2-naphthyl vibalate (0.15 mmol), cesium carbonate (0.2 mmol), and 1,4-dioxane (0.5 mL) were added in that order, and a Teflon (registered trademark) cap with packing was used. The test tube was closed and stirred for 24 hours while heating to 120 ° C. The yield of the desired coupling product 2- (2-naphthyl) benzoxazole was calculated by ¹ H NMR measurement using 1,1,2,2-tetrachloroethane as an internal standard.

  Table 5 shows the results of the effect of the phosphorus content of the polystyrene four-point crosslinked bisphosphine. With ligand 4, the reaction proceeded, but the target product remained in low yield. When ligand 3 was used, the desired product was obtained in good yield when the ratio of [4-t-butylstyrene / 1] was> 15. It is clear that copolymerization with an appropriate amount of styrene monomer is important for the expression of high catalytic activity by the polystyrene four-point bridged bisphosphine ligand. (See Figure 4)

反応条件：ベンゾオキサゾール（0.1 mmol）、ビバル酸 2-ナフチル（0.15 mmol）、Ni(cod)₂ (0.005 mmol, 5 mol%)、配位子（0.006 mmol, 6 mol%）、炭酸セシウム（0.2 mmol）、1,4-ジオキサン（1 mL）、24時間。

Reaction conditions: benzoxazole (0.1 mmol), 2-naphthyl vivalate (0.15 mmol), Ni (cod) ₂ (0.005 mmol, 5 mol%), ligand (0.006 mmol, 6 mol%), cesium carbonate (0.2 mmol), 1,4-dioxane (1 mL), 24 hours.

Nickel-catalyzed cross-coupling reaction between aryl chlorides and primary amines:
The Buchwald-Hartwig amination reaction of aryl halides is useful for the synthesis of aromatic amines contained in pharmaceuticals and functional electronic materials. Currently, palladium catalysts are frequently used. However, toxicity and performance degradation due to residual palladium in the product are often problematic, and alternatives to other metals are sought. In 2014, Hartwig et al. Reported that a nickel catalyst with 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (binap) was used for the cross-coupling reaction between aryl chlorides and primary amines. It was reported to be effective (reference: Hartwig, JF et al. J. Am. Chem. Soc. 2014, 136, 1617.). In this reaction, it has been proposed that nickel-binap 1: 1 type complexes are catalytically active species. Based on the idea that polystyrene four-point bridged bisphosphine is advantageous for the formation of metal-ligand 1: 1 type complexes based on the spatial isolation of metal coordination points, The immobilized nickel catalyst prepared in the reaction system from bisphosphine and Ni (cod) ₂ was found to be effective for the cross-coupling reaction of aryl chlorides and primary amines. Since the reaction hardly progresses with the polystyrene three-point bridged triarylphosphine 5 and 1,2-bis (diphenylphosphino) benzene, which are the inventors' prior inventions, the improvement of the catalytic activity by the fixation of bisphosphine is clear. is there.

In a nitrogen atmosphere, a 10 mL screw test tube was charged with a magnetic stir bar, ligand (0.003 mmol) and bis (1,5-cyclooctadiene) nickel (Ni (cod) ₂ ) (0.0025 mmol) in toluene ( 0.5 mL) was added, and the mixture was stirred at room temperature for 5 minutes. 4-Chlorotoluene (0.25 mmol), n-octylamine (0.375 mmol), sodium tert-butoxide (0.375 mmol) and toluene (0.5 mL) are added in that order, and the test tube is closed with a Teflon (registered trademark) cap with packing. The mixture was stirred for 20 hours while heating to 60 ° C. The yield of the desired coupling product, 4-methyl-N-octylaniline, was calculated by ¹ H NMR measurement using 1,1,2,2-tetrachloroethane as an internal standard. The results of the ligand effect are shown in Table 6. Further, the crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 90: 10), and the coupling product was isolated. Experiment number 35: Yield 36.3 mg, Yield 66%

Compound data for 4-methyl-N-octylaniline:
¹ H NMR (CDCl ₃ ): δ 0.87 (t, J = 7.2 Hz, 3H), 1.20-1.42 (m, 10H), 1.55-1.62 (m, 2H), 2.22 (s, 3H), 3.06 (t, J = 7.2 Hz, 2H), 3.44 (br-s, 1H), 6.50-6.54 (m, 2H), 6.97 (d, J = 8.0 Hz, 2H).
¹³ C NMR (CDCl ₃ ): δ 14.08, 20.35, 22.64, 27.17, 29.25, 29.41, 29.60, 31.82, 44.35, 112.85, 126.22, 129.66, 146.29.

反応条件：4-クロロトルエン（0.25 mmol）、n-オクチルアミン（0.375 mmol）、Ni(cod)₂ (0.0025 mmol, 1 mol%)、配位子（0.003 mmol, 1.2 mol%）、ナトリウム tert-ブトキシド（0.375 mmol）、トルエン（1 mL）、60℃、20時間。

Reaction conditions: 4-chlorotoluene (0.25 mmol), n-octylamine (0.375 mmol), Ni (cod) ₂ (0.0025 mmol, 1 mol%), ligand (0.003 mmol, 1.2 mol%), sodium tert- Butoxide (0.375 mmol), toluene (1 mL), 60 ° C., 20 hours.

Using immobilized catalysts prepared in the system from polystyrene four-point cross-linked bisphosphine 3 and Ni (cod) _2, we examined the substrate application range of aryl chlorides and primary amines in the Buchwald-Hartwig amination reaction. The coupling products shown in Table 7 were obtained. As the aryl chlorides, compounds having an electron donating group or an electron withdrawing group at the para position of the benzene ring are also applicable (Experiment No. 39, 40). This catalyst system is also excellent in tolerance against steric hindrance around the reaction point (Experiment Nos. 41 and 42). For amines substituted with a primary or secondary alkyl group, the reaction proceeded efficiently and gave the corresponding coupling product (Experiment Nos. 43, 44). For amines having tertiary alkyl groups, the reaction was carried out using lithium tert-butoxide as the base, and the desired product was obtained in good yield (Experiment No. 45).

Experiment No. 39: N, N-dimethyl-N-octylbenzene-1,4-diamine compound data:
¹ H NMR (CDCl ₃ ): δ 0.88 (t, J = 6.8 Hz, 3H), 1.28-1.38 (m, 10H), 1.59 (quint, J = 7.6 Hz, 2H), 2.81 (s, 6H), 3.05 (broad s, 2H), 3.15 (broad s, 1H), 6.61 (d, J = 8.0 Hz, 2H), 6.74 (d, J = 8.0 Hz, 2H).
¹³ C NMR (CDCl ₃ ): δ 14.10, 22.64, 27.21, 29.26, 29.43, 29.75, 31.82, 42.35, 45.11, 114.22, 115.98, 141.21, 143.95.
HRMS-ESI (m / z): [M] ⁺ cacld for C ₁₆ H ₂₈ O ₂ , 248.22470; found, 248.22509.

Experiment No. 40: Compound data for 4- (octylamino) -benzonitrile:
¹ H NMR (CDCl ₃ ): δ 0.88 (t, J = 6.4 Hz, 3H), 1.28-1.39 (m, 10H), 1.62 (quint, J = 7.2 Hz, 2H), 3.13 (t, J = 6.8 Hz , 2H), 4.22 (broad s, 1H), 6.54 (d, J = 5.2 Hz, 2H), 7.40 (d, J = 6.8 Hz, 2H).
¹³ C NMR (CDCl ₃ ): δ 14.04, 22.59, 26.97, 29.08, 29.16, 29.25, 31.73, 43.16, 98.14, 111.95, 120.57, 133.63, 151.41.
EI-MS (m / z): 230 ([M] ⁺ ).

Experiment No. 41: Compound data for 2,4,6-trimethoxy-N-octylamine:
¹ H NMR (CDCl ₃ ): δ 0.88 (t, J = 6.4 Hz, 3H), 1.27-1.35 (m, 10H), 1.49 (quint, J = 7.6 Hz, 2H), 3.05 (t, J = 6.8 Hz , 2H), 3.43 (broad s, 1H), 3.77 (s, 3H), 3.83 (s, 6H), 6.15 (s, 2H).
¹³ C NMR (CDCl ₃ ): δ 14.03, 22.61, 27.02, 29.25, 29.42, 30.51, 31.80, 48.05, 55.46, 55.79, 91.39, 121.08, 152.15, 154.57.
HRMS-ESI (m / z): [M + H] ⁺ cacld for C ₁₇ H ₃₀ O ₃ N, 296.22202; found, 296.22220.

Test Number 42: Compound data for 2,6-diisopropyl-N-octylaniline:
¹ H NMR (CDCl ₃ ): δ 0.89 (t, J = 6.4 Hz, 3H), 1.23-1.40 (m, 22H), 1.63 (quint, J = 6.8 Hz, 2H), 2.84-2.90 (m, 3H) , 3.26 (septet, J = 6.8 Hz, 2H), 7.02-7.10 (m, 3H).
¹³ C NMR (CDCl ₃ ): δ 14.10, 22.65, 24.26, 27.22, 27.64, 29.28, 29.51, 31.03, 31.84, 52.11, 123.46, 142.22, 143.69.
HRMS-ESI (m / z): [M + H] ⁺ cacld for C ₂₀ H ₃₆ N, 290.28423; found, 290.28420.

Experiment No. 43: Compound data for 4-methoxy-N-phenethylaniline:
¹ H NMR (CDCl ₃ ): δ 2.90 (t, J = 7.2 Hz, 2H), 3.35 (t + broad s, J = 6.8 Hz, 2H + 1H), 3.74 (s, 3H), 6.58 (d, J = 9.2 Hz, 2H), 6.78 (d, J = 9.2 Hz, 2H), 7.20-7.33 (m, 5H).
¹³ C NMR (CDCl ₃ ): δ 35.52, 45.97, 55.73, 114.32, 114.84, 126.33, 128.53, 128.74, 139.35, 142.16, 152.10.
EI-MS (m / z): 227 ([M] ⁺ ).

Test Number 44: Compound data for N-cyclohexyl-4-methoxyaniline:
¹ H NMR (CDCl ₃ ): δ 1.06-1.40 (m, 5H), 1.62-1.67 (m, 1H), 1.72-1.77 (m, 2H), 2.02-2.06 (m, 2H), 3.12-3.19 (m , 2H), 3.74 (s, 3H), 6.57 (d, J = 9.2 Hz, 2H), 6.76 (d, J = 8.8 Hz, 2H).
¹³ C NMR (CDCl ₃ ): δ 25.04, 25.94, 33.59, 52.72, 55.76, 114.75, 114.84, 141.57, 151.77.
EI-MS (m / z): 205 ([M] ⁺ ).

Experiment Number 45: Compound data for 4-methoxy-N- (1,1,3,3-tetramethylbutyl) -aniline:
¹ H NMR (400 MHz, CDCl ₃ ): δ 1.03 (s, 9H), 1.29 (s, 6H), 1.61 (s, 2H), 3.07 (broad s, 1H), 3.75 (s, 3H), 6.71- 6.76 (m, 4H).
¹³ C NMR (100.5 MHz, CDCl ₃ ): δ 30.09, 31.73, 54.32, 55.54, 55.75, 114.15, 121.10, 140.06, 153.35.
HRMS-ESI (m / z): [M + H] ⁺ cacld for C ₁₅ H ₂₆ ON, 236.20089; found, 236.20118.

Cobalt-catalyzed hydroboration of alkenes:
The hydroboration reaction of alkenes is a useful technique for obtaining alkyl boronic acid derivatives widely used as synthetic intermediates. So far, noble metals such as rhodium and iridium have been used as catalysts, but in recent years, the use of cheaper and abundant base metal catalysts has been demanded. In 2014, Huang et al. Reported that cobalt complex catalysts with optically active iminopyridine-oxazoline-type tridentate ligands are effective for asymmetric hydroboration of alkenes (reference: Huang, Z. et al. J. Am. Chem. Soc. 2014, 136, 15501.). The present inventor has found that a cobalt complex catalyst having polystyrene four-point cross-linked bisphosphine is effective for hydroboration of alkenes in the presence of a catalytic amount of sodium triethylborohydride as an additive. Since the reaction hardly progresses with the polystyrene three-point bridged triarylphosphine 5 and 1,2-bis (diphenylphosphino) benzene, which are the inventors' prior inventions, the improvement of the catalytic activity by the fixation of bisphosphine is clear. is there.

Under a nitrogen atmosphere, a magnetic stir bar, a ligand (0.003 mmol) and a solution of cobalt iodide (0.002 mmol) in tetrahydrofuran (0.4 mL) were added to a 10 mL screw test tube, and the mixture was stirred at room temperature for 5 minutes. Thereafter, sodium triethylborohydride (10 μL, 1 M THF solution, 0.01 mmol) was added, and the mixture was further stirred at room temperature for 10 minutes. α-methylstyrene (0.2 mmol) and pinacol borane (0.24 mmol) were sequentially added, the test tube was closed with a Teflon (registered trademark) packing cap, and the mixture was stirred at 25 ° C. for 16 hours. The yield of the target hydroboration product (2-phenylpropyl) boronic acid pinacol ester was calculated by ¹ H NMR measurement using 1,1,2,2-tetrachloroethane as an internal standard. The results of the ligand effect are shown in Table 8. Furthermore, the crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 95: 5), and the coupling product was isolated. Experiment number 47: Yield 31.0 mg, Yield 63%

Compound data for (2-phenylpropyl) boronic acid pinacol ester:
¹ H NMR (CDCl ₃ ): δ 1.12-1.17 (m, 14H), 1.26 (d, J = 6.9 Hz, 3H), 2.97-3.06 (m, 1H), 7.11-7.15 (m, 1H), 7.23- 7.30 (m, 4H).
¹³ C NMR (CDCl ₃ ): δ 21.21 (br), 24.65, 24.72, 24.87, 35.76, 82.92, 125.63, 126.57, 128.12, 149.17.

Reaction conditions: α-methylstyrene (0.2 mmol), pinacol borane (0.24 mmol), cobalt iodide (0.002 mmol, 1 mol%), ligand (0.003 mmol, 1.5 mol%), sodium triethylborohydride (0.01 mmol), tetrahydrofuran (0.4 mL), 25 ° C., 16 hours.

  The present invention is useful in the technical field related to transition metal complexes.

Claims (14)

A polymer transition metal complex represented by the following general formula (2).

In formula (2),

Is an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted aromatic heterohydrocarbon group (provided having 1 to 3 heteroatoms, the heteroatoms being nitrogen atoms, Selected from an oxygen atom and a sulfur atom),
R ¹ , R ² , R ³ and R ⁴ are each a linear or cross-linked polystyrene chain formed independently with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are bonded,
The crosslinked polystyrene chain may include at least one bisphosphine unit represented by the formula (3),

In formula (3),

Is synonymous with formula (2),
The phenyl group of the polystyrene chain is unsubstituted, or at least a part of the phenyl group of the polystyrene chain has a substituent,
M is a transition metal or a transition metal ion that can have a ligand. The transition metal or transition metal ion is at least one metal selected from the group consisting of a first transition element (3d transition element), a second transition element (4d transition element), and a third transition element (5d transition element) or The complex according to claim 1, which is a metal ion. The complex according to claim 1 or 2, wherein the aromatic hydrocarbon group is an aryl group, and the aromatic heterohydrocarbon group is a heteroaryl group. The substituent which the said aromatic hydrocarbon group, the said aromatic heterohydrocarbon group, and the phenylene group of the said polystyrene chain have is a C1-C6 alkyl group, The any one of Claims 1-3. Complex. The equivalent ratio of the bisphosphine unit represented by the general formula (3) and the styrene unit in the polystyrene chain represented by the R ¹ , R ² , R ³ , and R ⁴ is in the range of 1:10 to 1000. 5. The complex according to any one of 4. The complex according to any one of claims 1 to 5, wherein the ligand that M can have is alkene, halogen, carbonyl, hydroxy, nitro, amino, sulfonyl, or cyano. A step of mixing a polymer compound represented by the following general formula (1) and a compound containing a transition metal M to obtain a polymer transition metal complex represented by the following formula (2): Production method.

In formula (1),

Is an unsubstituted or substituted aromatic hydrocarbon group, or an unsubstituted or substituted aromatic heterohydrocarbon group (provided having 1 to 3 heteroatoms, the heteroatoms being nitrogen atoms, Selected from an oxygen atom and a sulfur atom),
R ¹ , R ² , R ³ and R ⁴ are each a linear or cross-linked polystyrene chain formed independently with a phenylene group to which R ¹ , R ² , R ³ and R ⁴ are bonded,
The crosslinked polystyrene chain may include at least one bisphosphine unit represented by the formula (4),

In formula (4),

Is synonymous with formula (1),
The phenyl group of the polystyrene chain is unsubstituted or at least a part of the phenyl group of the polystyrene chain has a substituent.

In the formula

The definitions of R ¹ , R ² , R ³ , and R ⁴ are the same as those defined in the general formula (1) except that R ¹ , R ² , R ³ , and R ⁴ are each formed with a phenylene group to which each is bonded. The bisphosphine unit that the polystyrene chain can contain at least one is represented by the formula (3):

In formula (3),

Is synonymous with formula (2),
M is a transition metal or a transition metal ion that can have a ligand. The method according to claim 7, wherein the aromatic hydrocarbon group is an aryl group, and the aromatic heterohydrocarbon group is a heteroaryl group. The production method according to claim 7 or 8, wherein the substituents of the aromatic hydrocarbon group, the aromatic heterohydrocarbon group, and the phenylene group of the polystyrene chain are alkyl groups having 1 to 6 carbon atoms. The compound containing a transition metal M includes a ligand that M may have, and the ligand is an alkene, halogen, carbonyl, hydroxy, nitro, amino, sulfonyl, or cyano. The manufacturing method of any one of these. The catalyst for organic compound coupling reactions containing the polymer transition metal complex in any one of Claims 1-6. The catalyst according to claim 11, wherein the organic compound coupling reaction is a C—H / C—O coupling reaction. The catalyst according to claim 11, wherein the organic compound coupling reaction is a CN cross-coupling reaction. The catalyst for hydroboration reaction containing the polymer transition metal complex of Claims 1-6.

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