JP6296231B2 - Solid catalyst - Google Patents

Description

  The present invention relates to a solid catalyst made of mesoporous organic silica, and more particularly to a solid catalyst made of mesoporous organic silica having a bipyridine group.

  It is known that an iridium complex coordinated with bipyridine can be used as a catalyst for a C—H boronation reaction of an aromatic compound (J. Am. Chem. Soc., 2002, Vol. 124, No. 3, 390-391 (Non-Patent Document 1)). As described in Non-Patent Document 1, when an iridium complex coordinated with bipyridine is used as a catalyst, an aromatic compound can be borated with a relatively high yield, and in particular, bis (pinacolato) diboron. In the boronation reaction of benzene with phenylboronic acid pinacol ester can be obtained with a very high yield of 95%. However, since the iridium complex coordinated with bipyridine is a homogeneous catalyst and has high solubility in an organic solvent, it is difficult to recover and reuse the catalyst after the boronation reaction. In addition, the iridium complex formed by mixing bipyridine and an iridium compound is unstable with respect to water and oxygen, and thus is difficult to isolate and handle in the atmosphere, and is an inert gas. It was necessary to prepare it in an atmosphere or in a reaction system. Furthermore, the iridium complex has the property of aggregating with the progress of the boronation reaction, and there has been a problem that the catalytic activity decreases with the progress of the reaction.

  Therefore, J.H. Synth. Org. Chem. , Jpn. 2011, Vol. 69, No. 11, pages 1212 to 1220 (Non-patent Document 2), bipyridinecarboxylic acid is coordinated as a heterogeneous catalyst in the C—H boronation reaction of aromatic compounds. Molecular iridium complexes are described. This high molecular weight iridium complex has high catalytic activity, and can boronate aromatic compounds in a relatively high yield, and can be recovered and reused. However, polymeric iridium complexes coordinated with bipyridinecarboxylic acid are unstable to water and oxygen, and are ignitable, so they cannot be handled in the atmosphere. However, there was a problem that the catalyst handled at 1 did not show any catalytic activity.

  In addition, J.H. Am. Chem. Soc. 2009, vol. 131, pages 5058-5059 (Non-patent Document 3) describes a phosphine-iridium complex supported on silica as a heterogeneous catalyst in a C—H boronation reaction of an aromatic compound. Yes. Since this phosphine-iridium complex is supported on silica, it can be recovered and reused. However, the phosphine-iridium complex supported on silica has a problem that the catalytic activity after recovery is lowered because the chemical structure in the vicinity of the active site is changed in the boronation reaction.

  On the other hand, Japanese Patent Application Laid-Open No. 2010-116512 (Patent Document 1) describes mesoporous organic silica in which a pyridine group or a bipyridine group is introduced into a skeleton, and this mesoporous organic silica is used as a metal ion or a metal complex. It is also described that it has excellent adsorption characteristics and support characteristics.

JP 2010-116512 A

T.A. Ishiyama et al. Am. Chem. Soc. 2002, Vol. 124, No. 3, 390-391 M.M. Nishida et al., J. MoI. Synth. Org. Chem. , Jpn. 2011, Vol. 69, No. 11, pages 1212-1220 S. Kawamorita et al., J. MoI. Am. Chem. Soc. 2009, vol. 131, pages 5058-5059.

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a solid catalyst containing a transition metal atom of Group 9 of the periodic table such as an iridium atom and having excellent catalytic activity. To do.

  As a result of intensive studies to achieve the above object, the present inventors have mixed mesoporous organic silica having a bipyridine group and a compound containing a transition metal atom of Group 9 of the periodic table such as an iridium atom. The compound containing the transition metal atom is immobilized on the outer surface of the mesoporous organic silica or the inner surface of the pores by forming a transition metal complex in which the bipyridine group is coordinated to the transition metal atom. Furthermore, the present inventors have found that the obtained transition metal-containing mesoporous organic silica has excellent catalytic activity, and completed the present invention.

  That is, the solid catalyst of the present invention has the following formula (1):

[In the formula (1), M represents a transition metal atom of Group 9 of the periodic table, L ¹ and L ² represent the same or different ligands, and at least one group of R ^{1 to} R ⁸ is The following formula (2):

(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. An organic group or a single bond; R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group; R ^b represents a hydrogen atom or a silyl group; k is 1 or 2; Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are present in the group represented by the formula (2). Independent, * is a binding site with an adjacent structure)
The remaining groups of R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, aryl group, alkoxy group, phenoxy group, acetyl group, benzoyl group, amino group A monovalent or divalent organic group selected from the group consisting of amide group, imide group, nitro group and cyano group]
Carbon-hydrogen, comprising a transition metal-containing mesoporous organic silica having a structure represented by formula (1), wherein the structure represented by the formula (1) is contained in the skeleton of the transition metal-containing mesoporous organic silica. It is a solid catalyst used in a boronation reaction involving bond cleavage .

In such a solid catalyst, M in the formula (1) is preferably an iridium atom .

In addition , at least one group of R ^{1 to} R ⁴ and at least one group of R ^{5 to} R ^{8 in} the formula (1) are each independently a group represented by the formula (2). it is not more preferable.

  Such a solid catalyst of the present invention is useful as a C—H bond activation catalyst. Here, the “C—H bond activation catalyst” is a catalyst that promotes a chemical reaction involving the cleavage of a carbon-hydrogen bond, and usually an organometallic compound is generated as a reaction intermediate or a transition state. Such chemical reactions involving carbon-hydrogen bond cleavage include boronation reactions of aromatic compounds such as benzene, boronation reactions of heterocyclic compounds such as pyridine, direct arylation of aromatic and heterocyclic compounds, Examples include alkylation.

  The reason why the solid catalyst of the present invention has an excellent catalytic activity is not necessarily clear, but the present inventors speculate as follows. That is, when a mesoporous organic silica having a bipyridine group and a compound containing a transition metal atom of Group 9 of the periodic table such as an iridium atom are mixed, the bipyridine group is coordinated to the transition metal atom to form a transition metal complex. It is speculated that the transition metal-containing mesoporous organic silica having the structure represented by the formula (1) acts as a solid catalyst by the catalytic action of the transition metal complex. In the mesoporous organic silica having a bipyridine group according to the present invention, the bipyridine group is incorporated in a highly dispersed state in the skeleton of the mesoporous organic silica, or is highly dispersed on the outer surface of the mesoporous silica or the inner surface of the pores. Therefore, it is presumed that the transition metal complex is also formed (immobilized) in a highly dispersed state on the outer surface of the transition metal-containing mesoporous organic silica or the inner surface of the pores. Thus, in the solid catalyst of the present invention, the catalytic activity site (the transition metal complex) is present in a highly dispersed state, so that it is presumed that excellent catalytic activity can be obtained. Further, since the highly dispersed transition metal complex hardly aggregates, it is presumed that the catalyst is hardly deactivated during the reaction, and excellent catalytic activity is maintained.

  In the solid catalyst of the present invention, the transition metal complex is immobilized in hydrophobic mesopores that are difficult for air (especially moisture) to enter, and the solid catalyst of the present invention is air (especially moisture). The solid catalyst of the present invention exhibits excellent stability against air (especially moisture) because the transition metal complex in the mesopores is not easily contacted with air (especially moisture) even when exposed to It is guessed.

  Furthermore, in the solid catalyst of the present invention, the bipyridine group is three-dimensionally strongly cross-linked by a siloxane bond, so that the transition metal complex is hardly detached due to mechanical action or chemical action. It is presumed that mechanical strength and chemical stability can be obtained. Moreover, since the leaching of the transition metal complex to the reaction system hardly occurs due to the three-dimensional crosslinking, it is presumed that the catalyst is hardly deactivated.

  According to the present invention, it is possible to obtain a solid catalyst that contains a transition metal atom of Group 9 of the periodic table such as an iridium atom and has excellent catalytic activity.

3 is a graph showing an X-ray diffraction pattern of a bipyridine group-containing organic silica mesoporous material obtained in Synthesis Example 1. FIG. 2 is a graph showing a nitrogen adsorption / desorption isotherm of a bipyridine group-containing organic silica mesoporous material obtained in Synthesis Example 1. FIG. 4 is a graph showing an X-ray diffraction pattern of a bipyridine group- and ethylene group-containing organic silica mesoporous material obtained in Synthesis Example 2. FIG. 5 is a graph showing nitrogen adsorption / desorption isotherms of a bipyridine group- and ethylene group-containing organic silica mesoporous material obtained in Synthesis Example 2. 6 is a graph showing an X-ray diffraction pattern of a bipyridine group-supported silica mesoporous material obtained in Synthesis Example 3. 6 is a graph showing a nitrogen adsorption / desorption isotherm of a bipyridine group-supported silica mesoporous material obtained in Synthesis Example 3. 6 is a graph showing an X-ray diffraction pattern of a bipyridine group-supported nonporous silica obtained in Synthesis Example 4. 6 is a graph showing a nitrogen adsorption / desorption isotherm of a bipyridine group-supported nonporous silica obtained in Synthesis Example 4. 6 is a graph showing an X-ray diffraction pattern of an iridium complex coordinated with a bipyridine group-containing organic silica mesoporous material obtained in Synthesis Example 5. FIG. It is a graph which shows the nitrogen adsorption-desorption isotherm of the iridium complex which the bipyridine group containing organic silica mesoporous body obtained in the synthesis example 5 coordinated. 2 is a graph showing an X-ray diffraction pattern of a solid component recovered after a boration reaction in Example 1. FIG. 2 is a graph showing a nitrogen adsorption / desorption isotherm of a solid component recovered after a boration reaction in Example 1. FIG. 4 is a graph showing an X-ray diffraction pattern of a solid component recovered after a boration reaction in Example 2. 4 is a graph showing a nitrogen adsorption / desorption isotherm of a solid component recovered after a boration reaction in Example 2. 4 is a graph showing an X-ray diffraction pattern of a solid component recovered after a boration reaction in Example 3. 4 is a graph showing a nitrogen adsorption / desorption isotherm of a solid component recovered after a boration reaction in Example 3. 4 is a graph showing an X-ray diffraction pattern of a solid component collected after each reaction of a boronation reaction repeatedly performed in Example 4. 6 is a graph showing nitrogen adsorption / desorption isotherms of solid components recovered after each of the boronation reactions repeatedly carried out in Example 4. FIG. 6 is a graph showing the pore size distribution of solid components recovered after each of the boronation reactions repeatedly performed in Example 4. FIG. It is a graph which shows the X-ray-diffraction pattern of the solid component collect | recovered after boronation reaction in Example 5. FIG. 6 is a graph showing a nitrogen adsorption / desorption isotherm of a solid component recovered after a boration reaction in Example 5. 4 is a graph showing an X-ray diffraction pattern of a solid component recovered after a boration reaction in Comparative Example 1 . 4 is a graph showing a nitrogen adsorption / desorption isotherm of a solid component recovered after a boration reaction in Comparative Example 1 .

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

<Solid catalyst>
First, the solid catalyst of the present invention will be described. The solid catalyst of the present invention has the following formula (1):

[In the formula (1), M represents a transition metal atom of Group 9 of the periodic table, L ¹ and L ² represent the same or different ligands, and at least one group of R ^{1 to} R ⁸ is The following formula (2):

(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. An organic group or a single bond; R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group; R ^b represents a hydrogen atom or a silyl group; k is 1 or 2; Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are present in the group represented by the formula (2). Independent, * is a binding site with an adjacent structure)
The remaining groups of R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, aryl group, alkoxy group, phenoxy group, acetyl group, benzoyl group, amino group A monovalent or divalent organic group selected from the group consisting of amide group, imide group, nitro group and cyano group]
It consists of transition metal containing mesoporous organic silica provided with the structure represented by these.

  In the solid catalyst of the present invention, the structure represented by the formula (1) is arranged on the outer surface as long as it is arranged on the inner surface (pore wall) of the transition metal-containing mesoporous organic silica. Or may be contained in the skeleton of the transition metal-containing mesoporous organic silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “first transition metal-containing mesoporous organic silica”). The transition metal-containing mesoporous organic silica may be bonded to the inner surface (pore wall) of the mesoporous silica (hereinafter, this transition metal-containing mesoporous organic silica is also referred to as “second transition metal-containing mesoporous organic silica”).

  The solid catalyst of the present invention contains a bipyridine group as represented by the formula (1), and a transition metal complex is formed by coordination of the bipyridine group to the transition metal atom. The complex becomes an active site and exhibits catalytic action. In the solid catalyst of the present invention, it is not necessary that all bipyridine groups are coordinated to the transition metal atom. In the first transition metal-containing mesoporous organic silica, the group represented by the formula (2) is a group having a crosslinking point (hereinafter also referred to as “crosslinking group”), and the siloxane in the crosslinking group Since the bipyridine group is three-dimensionally cross-linked by the bond (Si—O bond), the solid catalyst of the present invention exhibits high durability against mechanical action and chemical action.

In the formula (1), M represents a transition metal atom of Group 9 of the periodic table, L ¹ and L ² represent a ligand, and these may be the same or different. Such a ligand is not particularly limited as long as it is coordinated to the transition metal atom. For example, oxygen-based ligands such as a methoxy group, an ethoxy group, a phenoxy group, a hydroxyl group, and an acetoxy group , 1,5-cyclooctadiene, cis-cyclooctene, tetramethylcyclopentadiene, cymene and other carbon-based ligands, trimethylphosphine, tributylphosphine, trialkylphosphine, triphenylphosphine, etc. Examples of the ligand include nitrogen ligands such as ligands, cyclohexyl diamine, and alkyl amines. Among such ligands, from the viewpoint of improving the electron density on the iridium center atom, an electron donating ligand is preferable, and a methoxy group and 1,5-cyclooctadiene are more preferable.

In the formula (1), at least one group of R ^{1 to} R ⁸ is a crosslinking group represented by the formula (2). In the case where the solid catalyst of the present invention is composed of the first transition metal-containing mesoporous organic silica, from the viewpoint that a mesoporous structure is easily formed, at least one group of R ^{1 to} R ⁴ and It is preferable that at least one group among R ^{5 to} R ⁸ is independently the crosslinking group, and it is more preferable that R ² and R ⁶ are each independently the crosslinking group. Further, when the solid catalyst of the present invention is composed of the second transition metal-containing mesoporous organic silica, from the viewpoint of ease of bonding, one group of R ^{1 to} R ⁸ is bonded to the bridge. A group is preferable, and one of R ² and R ⁶ is more preferably the cross-linking group.

  Y in the formula (2) is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) or an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). ), An alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an arylene group (preferably having 6 to 12 carbon atoms), an ether group, a carbonyl group, an amino group, an amide group, and an imide group. A divalent or trivalent organic group or a single bond selected from the group consisting of

  Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group. Examples of the alkynylene group include an ethynylene group, Examples of the arylene group include monocyclic aromatic rings such as a phenylene group, and aromatic condensed rings such as a naphthylene group and a fluorenylene group.

  Among these divalent or trivalent organic groups and single bonds, an alkylene group and a single bond are preferable from the viewpoint of improving the mechanical strength and chemical stability of the solid catalyst, and alkylene having 1 to 6 carbon atoms. Groups and single bonds are more preferred.

R ^a in the formula (2) represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) or a substituted or unsubstituted allyl group, and the allyl group has a substituent such as a methyl group. It may be. In the formula (2), R ^b represents a hydrogen atom or a silyl group, and examples of the silyl group include alkylsilyl groups such as a trimethylsilyl group, and R ^b is said to improve chemical stability. From the viewpoint, an alkylsilyl group is preferable, and a trimethylsilyl group is more preferable.

  Moreover, * in the said Formula (2) is a coupling | bond part with an adjacent structure. When the solid catalyst of the present invention is composed of the first transition metal-containing mesoporous organic silica, the adjacent structure is represented by the formula (1) in the transition metal-containing mesoporous organic silica. In the case where the solid catalyst of the present invention is composed of the second transition metal-containing mesoporous organic silica, the mesoporous silica is exemplified. The bonding site is preferably bonded to a silicon atom on the surface of the mesoporous silica.

  In the formula (2), k is 1 or 2, i is an integer of 1 to 3 (preferably an integer of 2 to 3), and j is an integer of 0 to 2 (preferably an integer of 0 to 1). And 1 ≦ i + j ≦ 3 (preferably 2 ≦ i + j ≦ 3). Note that the combination of i and j is independent for each of a plurality of the crosslinking groups, and need not be the same for all the crosslinking groups in the solid catalyst of the present invention.

In the formula (1), the remaining groups of R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 6 carbon atoms). 12), an alkoxy group (preferably having a carbon number of 1 to 12), a phenoxy group, an acetyl group, a benzoyl group, an amino group, an amide group, an imide group, a nitro group and a cyano group. Is an organic group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a monocyclic aromatic ring such as a phenyl group, and an aromatic condensed ring such as a naphthyl group and a fluorenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Among these monovalent or divalent organic groups, from the viewpoint of improving the mechanical strength and chemical stability of the solid catalyst, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, and a phenoxy group Preferably, a hydrogen atom is more preferable.

  In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the ratio of the structure represented by the formula (1) is not particularly limited as long as it is 1% by mass or more. 10-100 mass% is preferable about a said 1st transition metal containing mesoporous organic silica from a viewpoint of improving, 30-100 mass% is more preferable, 50-100 mass% is further more preferable, 70-100 mass% Is particularly preferable, and 100% by mass is most preferable. The second transition metal-containing mesoporous organic silica is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and further preferably 10 to 60% by mass. ˜50 mass% is particularly preferred.

  When the proportion of the structure represented by the formula (1) is less than 100% by mass, the structure other than the structure represented by the formula (1) (hereinafter referred to as “other structure”) may be an organosilane described later. Examples include a structure derived from a compound (preferably alkoxysilane), and the following formula (3):

The structure represented by these is preferable.

In the formula (3), R ⁹ is a divalent to tetravalent organic group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an arylene group (preferably having 6 carbon atoms). ~ 12) and the like. R ^c each independently represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) or a substituted or unsubstituted allyl group, and the allyl group may have a substituent such as a methyl group. R ^d each independently represents a hydrogen atom or a silyl group, and examples of the silyl group include alkoxysilyl groups such as a methoxysilyl group, and R ^d is an alkoxysilyl group from the viewpoint of improving chemical stability. Group is preferred, and a methoxysilyl group is more preferred.

  Moreover, * in the said Formula (3) is a coupling | bond part with an adjacent structure. Examples of the adjacent structure include a repeating unit composed of the structure represented by the formula (1) in the transition metal-containing mesoporous organic silica, a repeating unit derived from an organosilane compound described later, and a surface structure of mesoporous silica (preferably Is a silicon atom on the surface of mesoporous silica).

  In the formula (3), each r is independently 1 or 2, p is each independently an integer of 1 to 3 (preferably an integer of 2 to 3), and q is each independently an integer of 0 to 2. (Preferably an integer of 0 to 1) and 1 ≦ p + q ≦ 3 (preferably 2 ≦ p + q ≦ 3). In addition, the combination of p and q is independent in each of the structures represented by the above formula (3), and is the same in all the structures represented by the above formula (3) in the solid catalyst of the present invention. Need not be.

  In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the ratio of such other structures is 99 with respect to the total amount with the structure represented by the formula (1). Although there will be no restriction | limiting in particular if it is below mass%, From a viewpoint that catalyst activity improves, 0-90 mass% is preferable, 0-70 mass% is more preferable, 0-50 mass% is more preferable, 0-30 Mass% is particularly preferred.

The transition metal-containing mesoporous organic silica according to the present invention has a structure having mesopores (mesopore structure). The pore diameter (center pore diameter) in such a mesopore structure is preferably 1 to 50 nm, and more preferably 2 to 30 nm. Moreover, as pore volume, 0.1 cm < ³ > / g or more is preferable and 0.3 cm < ³ > / g or more is more preferable. When the central pore diameter and pore volume are less than the lower limits, the reaction substrate in the catalytic reaction does not sufficiently diffuse into the mesopores, and the catalytic reaction tends not to proceed sufficiently. Further, in the transition metal-containing mesoporous organic silica, the BET specific surface area is preferably 100 cm ² / g or more, and more preferably 300 cm ² / g or more. When the BET specific surface area is less than the lower limit, sufficient catalytic activity tends not to be obtained.

  The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the sample was cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas was introduced, the adsorption amount was determined by the constant volume method or gravimetric method, and then the pressure of the introduced nitrogen gas was gradually increased, Plot the adsorption amount of nitrogen gas against the equilibrium pressure to obtain the adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, or BJH method.

  In the X-ray diffraction pattern of the transition metal-containing mesoporous organic silica according to the present invention, it is preferable that one or more diffraction peaks exist at a diffraction angle corresponding to a d value of 1 to 50 nm. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle exists in the sample. Therefore, the presence of one or more diffraction peaks at a diffraction angle corresponding to a d value of 1 to 50 nm indicates that a regular mesopore structure in which pores are regularly arranged at intervals of 1 to 50 nm. It means to have. The transition metal-containing mesoporous organic silica having such a regular mesoporous structure has excellent catalytic activity because the transition metal complex is stably immobilized.

  Such a solid catalyst of the present invention includes, for example, the following formula (1a):

[In the formula (1a), R ^{1 to} R ⁸ are the same groups as R ^{1 to} R ⁸ in the formula (1)].
It can manufacture by mixing the mesoporous organic silica provided with the structure represented by the compound containing the transition metal atom of the periodic table 9th group. Thereby, the nitrogen atom in the said formula (1a) coordinates to the said transition metal atom, and the transition metal containing mesoporous organic silica represented by the said Formula (1) is obtained. Such mixing may be performed in a system different from the catalytic reaction system before the catalytic reaction, or may be performed in the catalytic reaction system.

Examples of the compound containing a transition metal atom include the following formula (5):
L ¹ -ML ²
(Formula (5) in, M, ^{L 1} and ^{L 2} are those wherein Formula (1) M, the same as ^{L 1} and ^{L 2)}
The transition metal compound represented by these is preferable. Specific examples of the transition metal compound include di-μ-methoxybis (1,5-cyclooctadiene) diiridium (I), di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I), Examples include di-μ-hydroxybis (1,5-cyclooctadiene) diiridium (I), di-μ-phenoxybis (1,5-cyclooctadiene) diiridium (I), and the like.

  In the mesoporous organic silica having the structure represented by the formula (1a), if the structure represented by the formula (1a) is disposed on the pore inner surface (pore wall) of the mesoporous organic silica, The mesoporous organic silica may be disposed on the outer surface or may be contained in the skeleton of the mesoporous organic silica (hereinafter, this mesoporous organic silica is also referred to as “first mesoporous organic silica”). It may be bonded to the pore inner surface (pore wall) of silica (hereinafter, this mesoporous organic silica is also referred to as “second mesoporous organic silica”).

Moreover, as mentioned above, R ^{1 to} R ⁸ in the formula (1a) are the same groups as R ^{1 to} R ⁸ in the formula (1), but the binding site * in the formula (2) In the first mesoporous organic silica as the adjacent structure bonded to the repeating unit, a repeating unit composed of the structure represented by the formula (1a) in the mesoporous organic silica or a repeating unit derived from an organosilane compound described later In the second mesoporous organic silica, the surface structure of the mesoporous silica may be mentioned, and the binding site is preferably bonded to a silicon atom on the surface of the mesoporous silica.

  In the mesoporous organic silica having the structure represented by the formula (1a), the ratio of the structure represented by the formula (1a) is not particularly limited as long as it is 1% by mass or more. From the viewpoint of increasing the content of the complex coordinated to the metal atom and improving the catalytic activity, the first mesoporous organic silica is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and 50 To 100% by mass is more preferable, 70 to 100% by mass is particularly preferable, 100% by mass is most preferable, and the second mesoporous organic silica is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, 10-60 mass% is further more preferable, and 15-50 mass% is especially preferable.

  When the ratio of the structure represented by the formula (1a) is less than 100% by mass, the structure other than the structure represented by the formula (1a) (hereinafter referred to as “other structure”) is an organosilane described later. Examples include a structure derived from a compound (preferably alkoxysilane), and a structure represented by Formula (3) is preferable.

  In the mesoporous organic silica having the structure represented by the formula (1a), the ratio of such other structures is 99% by mass or less with respect to the total amount with the structure represented by the formula (1a). If it is, there will be no restriction | limiting in particular, From a viewpoint that catalyst activity improves, 0-90 mass% is preferable, 0-70 mass% is more preferable, 0-50 mass% is more preferable, 0-30 mass% is Particularly preferred.

  The first mesoporous organic silica may be represented by the following formula (1b):

[At least one group of R ^{1 to} R ⁸ in the formula (1b) is represented by the following formula (2a):

(In the formula (2a), Y and R ^a are the same groups as Y and R ^a in the formula (1), R ^e represents an alkyl group having 1 to 8 carbon atoms, and k represents the above formula ( 2) is the same as k in s, and s is an integer of 0 to 3)
A group represented by the formula (2) by hydrolysis / condensation polymerization, and the remaining groups of R ^{1 to} R ⁸ in the formula (1b) are the above-mentioned groups It is the same group as the group other than the crosslinking group represented by the formula (2) in the formula (1) and the formula (1a)]
It can manufacture by hydrolyzing and polycondensing the organosilane compound (henceforth "bipyridine group containing organosilane compound") provided with the structure represented by these.

  In addition, the second mesoporous organic silica is formed by adding the bipyridine to silanol groups on the outer surface of the normal mesoporous silica (including mesoporous organic silica containing an organic group other than the bipyridine group) and the inner surface of the pore (pore wall). It can be produced by hydrolyzing and condensing a group-containing organosilane compound.

R ^e in the formula (2a) is an alkyl having 1 to 4 carbon atoms such as a methyl group, an ethyl group, or an isopropyl group from the viewpoint that the bipyridine group-containing organic silane compound is easily hydrolyzed / condensed (heavy). Group is preferable, and a methyl group, an ethyl group, and an isopropyl group are more preferable. In addition, when R ^a is an allyl group, the allyl group is eliminated by hydrolysis, so the value of (3-s) in the formula (2a) and (3-i-j) in the formula (2) The values of do not necessarily match.

Such bipyridine group-containing organosilane compounds may be used alone or in combination of two or more. Of these bipyridine group-containing organosilane compounds, when the first mesoporous organic silica is produced, the substituent represented by the formula (2a) is easily introduced, and the obtained first mesoporous compound is obtained. From the viewpoint that a mesopore structure is easily formed in organic silica, at least one group (more preferably R ² ) of R ^{1 to} R ⁴ and more preferably R ^{5 to} R ^{8 in} the formula (1b). At least one group (more preferably R ⁶ ) is each independently a group represented by the formula (2a), and the remaining groups among R ^{1 to} R ⁸ are a hydrogen atom, a methyl group, an ethyl group, a methoxy group Group, a phenyl group and a phenoxy group (more preferably a hydrogen atom), and Y in the formula (2a) is either an alkylene group or a single bond (more preferably Is preferably a bipyridine group-containing organosilane compound which is a single bond. Moreover, from the viewpoint that the degree of crosslinking of the obtained first mesoporous organic silica can be increased and the structure can be stabilized, s in the formula (2a) is preferably 2 or 3, and particularly preferably 3.

On the other hand, in the case of producing the second mesoporous organic silica, the substituent represented by the formula (2a) is easily introduced, and the mesoporous silica and the bipyridine group-containing organosilane compound are easily bonded. In the formula (1b), one of R ^{1 to} R ⁸ (more preferably one of R ² and R ⁶ ) is a group represented by the formula (2a), Bipyridine group-containing organosilane compounds in which Y in formula (2a) is either an alkylene group or a single bond (more preferably an alkylene group having 1 to 6 carbon atoms) are preferred. Further, from the viewpoint of increasing the bond strength between mesoporous silica and the bipyridine group-containing organosilane compound, s in the formula (2a) is preferably 2 or 3, and particularly preferably 3.

  When producing mesoporous organic silica having the structure represented by the formula (1a), the ratio of the bipyridine group-containing organic silane compound in the total organic silane compound as a raw material is particularly limited as long as it is 1% by mass or more. However, from the viewpoint that the amount of the bipyridine group coordinated to the transition metal atom in the obtained mesoporous organic silica is increased and the catalytic activity is improved, 10 to 100% by mass is preferable, and 30 to 100% by mass is more preferable. Preferably, 50-100 mass% is further more preferable, 70-100 mass% is especially preferable, and 100 mass% is the most preferable.

  In the case of producing the second mesoporous organic silica, the mixing ratio of the bipyridine group-containing organic silane compound and mesoporous silica is such that the bipyridine group-containing organic silane compound is 15 parts per 100 parts by mass of mesoporous silica. -400 parts by mass, more preferably 20-250 parts by mass, even more preferably 25-150 parts by mass, and particularly preferably 30-100 parts by mass.

  When the ratio of the bipyridine group-containing organic silane compound in the total organic silane compound as a raw material is less than 100% by mass, an organic silane compound other than the bipyridine group-containing organic silane compound (hereinafter referred to as “other organic silane compound”) Dialkoxysilanes such as dimethoxysilane and diethoxysilane; trialkoxysilanes such as trimethoxysilane and triethoxysilane; tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; 1,2-bis (triethoxysilyl) ethane; Organics such as 1,2-bis (triethoxysilyl) ethylene, 1,2-bis (triethoxysilyl) acetylene, 1,4-bis (triethoxysilyl) benzene, 4,4′-bis (triethoxysilyl) biphenyl Group cross-linking alkoxy Known alkoxysilane compounds such as silane. These alkoxysilane compounds may be used alone or in combination of two or more.

  Among such other organosilane compounds, the following formula (3a):

An organic group-crosslinked alkoxysilane represented by the formula is preferred.

In the formula (3a), which is the same group as ^{R 9} and ^{R c} of ^{R 9} and ^{R c} above formula (3). R ^f independently represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group or an isopropyl group, and more preferably a methyl group, an ethyl group or an isopropyl group. r is the same as r in the formula (3), and t is independently an integer of 0 to 3 (preferably an integer of 1 to 3, more preferably an integer of 2 to 3). In addition, when R ^c is an allyl group, the allyl group is eliminated by hydrolysis. Therefore, the value of (3-t) in the formula (3a) and (3-pq) in the formula (3) are used. The values of do not necessarily match.

  The ratio of the other organic silane compound in the total organic silane compound as a raw material is not particularly limited as long as it is 99% by mass or less, but the bipyridine group coordinated to the transition metal atom in the obtained mesoporous organic silica. From the viewpoint of increasing the amount and improving the catalyst activity, 0 to 90% by mass is preferable, 0 to 70% by mass is more preferable, 0 to 50% by mass is further preferable, and 0 to 30% by mass is particularly preferable.

  The conditions for the hydrolysis / condensation (heavy) combination are not particularly limited, but it is preferable that the organic silane compound is hydrolyzed and condensed (heavy) in the presence of an acid or base catalyst in a solvent. Examples of the solvent used at this time include alcohol, tetrahydrofuran, an organic solvent of acetone, water, and a mixed solvent thereof. Although there is no restriction | limiting in particular as a density | concentration of the said organosilane compound in a solution, 0.05-5 mass% is preferable.

  Examples of the acid catalyst include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and the solution in the case of using the acid catalyst is preferably acidic with a pH of 6 or less (more preferably 2 to 5). . Furthermore, examples of the base catalyst include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like. When the base catalyst is used, the solution has a basic pH of 8 or more (more preferably 9 to 11). Preferably there is.

  Various conditions (temperature, time, etc.) in the hydrolysis / condensation (height) are not particularly limited, and are appropriately selected according to the organic silane compound to be used, the target mesoporous organic silica, etc. The organosilane compound can be hydrolyzed and polycondensed at a temperature of about 150 ° C. for a time of about 30 minutes to 72 hours.

  Moreover, when manufacturing said 1st mesoporous organic silica, in addition to the organic silane compound which is a raw material, surfactant is mixed. Thereby, mesopores can be formed in the obtained organic silica. That is, a surfactant micelle or liquid crystal structure is used as a template to form organic silica having mesopores.

  Such a surfactant is not particularly limited and may be any of cationic, anionic and nonionic, specifically, alkyltrimethylammonium, alkyltriethylammonium, dialkyldimethylammonium, benzylammonium. Examples thereof include chlorides, bromides, iodides or hydroxides; fatty acid salts, alkyl sulfonates, alkyl phosphates, polyethylene oxide nonionic surfactants, primary alkyl amines, and the like. These surfactants may be used alone or in combination of two or more.

Among the surfactants, examples of the polyethylene oxide nonionic surfactant include a polyethylene oxide nonionic surfactant having a hydrocarbon group as a hydrophobic component and polyethylene oxide as a hydrophilic portion. Such surfactants, for example, the general formula _{C n H 2n + 1 (OCH} 2 CH 2) expressed in m OH, n is 10 to 30, m can be preferably used those which are 1 to 30. Further, esters of fatty acids such as oleic acid, lauric acid, stearic acid, and palmitic acid and sorbitan, or compounds obtained by adding polyethylene oxide to these esters can also be used as the polyethylene oxide nonionic surfactant.

Furthermore, a triblock copolymer type polyalkylene oxide can also be used as the polyethylene oxide nonionic surfactant. Examples of such surfactants include those composed of polyethylene oxide (EO) and polypropylene oxide (PO) and represented by the general formula (EO) _x (PO) _y (EO) _x . x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is preferably 13 to 106, and y is more preferably 29 to 70. Examples of the triblock copolymer include (EO) ₁₉ (PO) ₂₉ (EO) ₁₉ , (EO) ₁₃ (PO) ₇₀ (EO) ₁₃ , (EO) ₅ (PO) ₇₀ (EO) ₅ , (EO) _13. (PO) ₃₀ (EO) ₁₃ , (EO) ₂₀ (PO) ₃₀ (EO) ₂₀ , (EO) ₂₆ (PO) ₃₉ (EO) ₂₆ , (EO) ₁₇ (PO) ₅₆ (EO) ₁₇ , (EO ) ₁₇ (PO) ₅₈ (EO) ₁₇ , (EO) ₂₀ (PO) ₇₀ (EO) ₂₀ , (EO) ₈₀ (PO) ₃₀ (EO) ₈₀ , (EO) ₁₀₆ (PO) ₇₀ (EO) ₁₀₆ , (EO) ₁₀₀ (PO) ₃₉ (EO) ₁₀₀ , (EO) ₁₉ (PO) ₃₃ (EO) ₁₉ , (EO) ₂₆ (PO) ₃₆ (EO) ₂₆ may be mentioned. These triblock copolymers are available from BASF, Aldrich, etc., and triblock copolymers having desired x and y values can be obtained at a small scale production level.

Further, a star diblock copolymer in which two polyethylene oxide (EO) chains-polypropylene oxide (PO) chains are bonded to two nitrogen atoms of ethylenediamine can also be used as the polyethylene oxide nonionic surfactant. Examples of such star diblock copolymers include those represented by the general formula ((EO) _x (PO) _y ) ₂ NCH ₂ CH ₂ N ((PO) _y (EO) _x ) ₂ . Here, x and y represent the number of repetitions of EO and PO, respectively, x is preferably 5 to 110, y is preferably 15 to 70, x is 13 to 106, and y is 29 to 70. preferable.

Among such surfactants, a salt (preferably a halide salt) of alkyltrimethylammonium [C _p H _{2p + 1} N (CH ₃ ) ₃ ] from the viewpoint that a mesoporous organic silica having regular mesopores can be obtained. ) Is preferably used. In that case, the alkyl group in the alkyltrimethylammonium preferably has 8 to 22 carbon atoms. Examples include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, octyltrimethylammonium bromide, docosyltrimethylammonium chloride, and the like.

  The first mesoporous organic silica forms an organosilica mesostructure containing the surfactant by hydrolyzing and polycondensating the organosilane compound in a solution containing such a surfactant. Then, it can manufacture by removing the said surfactant from this organosilica mesostructure.

  The concentration of the surfactant in the solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass. When the concentration of the surfactant is less than the lower limit, the formation of pores tends to be incomplete. On the other hand, when the concentration exceeds the upper limit, the amount of the surfactant remaining in the solution increases, resulting in uniform pores. Tend to decrease. Moreover, as content of surfactant in the said organic silica mesostructure, 20-90 mass% is preferable, and 30-70 mass% is more preferable. When the surfactant content is less than the lower limit, the order of the mesopore structure tends to be lowered, and when the upper limit is exceeded, the mesopore uniformity tends to be lowered.

  As a method of removing the surfactant, for example, (i) a method of removing the surfactant by immersing the organic silica mesostructure in an organic solvent (for example, ethanol) having high solubility in the surfactant, (Ii) a method of removing the surfactant by baking the organosilica mesostructure at 250 to 550 ° C., (iii) immersing the organosilica mesostructure in an acidic solution (for example, dilute hydrochloric acid) and heating, An ion exchange method in which a surfactant is exchanged with hydrogen ions; (iv) the organic silica mesostructure is exposed to a heated acidic vapor (for example, hydrochloric acid vapor) and then immersed in an organic solvent (for example, ethanol) And a method of eluting the surfactant in an organic solvent. The treatment conditions in these methods can be appropriately set depending on the type of surfactant, organic solvent, acidic vapor to be used.

  In the hydrolysis / condensation (poly) reaction of the organosilane compound, the silyl group in the formula (2a) and the formula (3a) is usually hydrolyzed to form a silanol group (Si—OH). Then, a siloxane bond (Si—O—Si) is formed by a subsequent condensation (heavy) reaction. At this time, a part of the silanol group may not be converted into a siloxane bond and may remain as it is. Since the mesoporous organic silica in which the silanol group remains tends to form an unnecessary iridium complex with the transition metal compound, the obtained bipyridine group-containing mesoporous organic silica is reacted with N-trimethylsilylimidazole, trimethylsilyl chloride, or the like. Thus, it is preferable to protect the silanol group.

<Boronization reaction>
Next, the boronation reaction of an aromatic compound using the solid catalyst of the present invention will be described. The solid catalyst of the present invention is useful as a catalyst for an aromatic compound boronation reaction. There is no restriction | limiting in particular as reaction conditions of such a boronation reaction, The reaction conditions of the conventional boronation reaction can be employ | adopted as it is.

  The aromatic compound is not particularly limited, and examples thereof include monocyclic aromatic compounds such as benzene, monocyclic heterocyclic aromatic compounds such as thiophene, furan, and pyridine, benzofuran, indole, benzothiophene, benzodithiophene, Examples include condensed ring type heteroaromatic compounds such as thienothiophene and dithienothiophene, and polycyclic aromatic compounds in which two or more aromatic rings such as bithiophene, terthiophene, and trithiophenylphenylamine are linked by a single bond. It is done. Some of the hydrogen atoms in the aromatic ring may be halogen atoms (for example, chlorine atoms, bromine atoms), alkyl groups (for example, methyl groups), halogenated alkyl groups (for example, fluoromethyl groups), alkoxy groups (for example, , A methoxy group), a carboxylic acid ester group (for example, an acetoxy group) and the like.

  Examples of the boronating agent used in the boronation reaction include pinacol borane, bis (pinacolato) diboron, bis (neopentylglycolate) diboron, and bis (catecholate) diboron.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Synthesis Example 1)
<Synthesis of bipyridine group-containing mesoporous organic silica>
Octadecyltrimethylammonium chloride (C ₁₈ TMACl, 3.78 g, 10.8 mmol), distilled water (202 ml) and 6N aqueous sodium hydroxide solution (0.590 ml, 3.54 mmol) were mixed and heated to 50 ° C. to obtain The mixture was stirred vigorously while 5,5′-bis (triisopropoxysilyl) -2,2′-bipyridine (Si-BPy-Si, 4.59 g, 8.12 mmol) in ethanol (9.17 ml). ) Was added dropwise over 90 minutes. The resulting solution was stirred vigorously for 3 days while being heated at 50 ° C., and was further allowed to stand for 3 days while being heated at 50 ° C., and the following reaction formula (I):

The reaction represented by The produced precipitate was collected by pressure filtration to obtain a bipyridine group-containing organic silica mesostructure containing a template surfactant (C ₁₈ TMACl). The organosilica mesostructure is added to acidic ethanol (mixed solution of ethanol 346 ml and 2M hydrochloric acid 10.2 ml) and suspended overnight to remove the template surfactant, and the bipyridine group which is a light yellow to gray solid Containing mesoporous organic silica (yield 1.65 g) was obtained. In order to protect silanol groups remaining on the outer surface and pore surface of this mesoporous organic silica, N-trimethylsilylimidazole (3 ml) was added to the bipyridine group-containing mesoporous organic silica (650 mg) under an argon atmosphere. The resulting mixture was stirred at 60 ° C. for 12 hours, and the following reaction formula (II):

The reaction product was cooled to 0 ° C. and then added to methanol to stop the reaction. The resulting pale yellow suspension was filtered under reduced pressure using a membrane filter (pore size 0.5 μm), and the filter cake was dried to give a pale yellow powdered bipyridine group-containing mesoporous organic silica (TMS-1, yield 650 mg, Si -BPy-Si structure content 100 mass%) was obtained.

When the X-ray diffraction pattern of this mesoporous organic silica TMS-1 was measured using a powder X-ray diffractometer (“RINT-2200” manufactured by Rigaku Corporation), 2θ = 1.80 ° as shown in FIG. 1A. A diffraction peak derived from a regular mesostructure was observed at (d = 4.90 nm). Further, diffraction derived from a layered arrangement structure of bipyridine groups at 2θ = 11.6 ° (d = 0.76 nm), 15.2 ° (d = 0.58 nm), and 23.0 ° (d = 0.39 nm). A peak was observed. In addition, the nitrogen adsorption / desorption isotherm of the mesoporous organic silica TMS-1 was measured using an automatic specific surface area / pore distribution measuring device (“Autosorb-1 system” manufactured by Cantachrome) under conditions of liquid nitrogen temperature (−196 ° C.). As shown in FIG. 1B, it was IV type as determined by the constant volume gas adsorption method. Therefore, it was confirmed from the X-ray diffraction pattern and nitrogen adsorption / desorption isotherm that the mesoporous organic silica TMS-1 has regular mesopores. Further, the specific surface area of this mesoporous organic silica TMS-1 was calculated by the BET method to be 520 m ² / g, the central pore diameter was calculated by the BJH method to be 21.9 mm, and the pore volume was t -It was 0.20 cm < ³ > / g when computed by the plot test.

(Synthesis Example 2)
<Synthesis of bipyridine group and ethylene group-containing mesoporous organic silica>
Octadecyltrimethylammonium chloride (C ₁₈ TMACl, 300 mg, 0.86 mmol), distilled water (53 ml) and 6N aqueous sodium hydroxide solution (0.530 ml, 3.18 mmol) were mixed, and the resulting mixture was stirred vigorously. 1,2-bis (triethoxysilyl) ethane (Si-Et-Si, 888 mg, 2.50 mmol) was added dropwise over 3 minutes, stirred at room temperature for 20 minutes, and then 5,5′-bis (triiso An ethanol solution (2 ml) of propoxysilyl) -2,2′-bipyridine (Si-BPy-Si, 300 mg, 0.53 mmol) was added dropwise over 30 minutes. The resulting suspension was stirred for 2 hours using an ultrasonic stirrer while being heated at 50 ° C., then vigorously stirred for 2 days while being heated at 50 ° C., and then allowed to stand for 3 days while being heated at 50 ° C. The following reaction formula (III):

The reaction represented by The produced precipitate was collected by pressure filtration to obtain a bipyridine group-containing ethylene silica-containing organic silica mesostructure containing a template surfactant (C ₁₈ TMACl). This organosilica mesostructure is added to acidic ethanol (mixed solution of 100 ml of ethanol and 2.8 ml of 2M hydrochloric acid) and suspended overnight to remove the template surfactant, and contains a bipyridine group and an ethylene group as a light yellow solid. Mesoporous organic silica (yield 643 mg) was obtained. In order to protect the silanol groups remaining on the outer surface and pore surface of this mesoporous organic silica, N-trimethylsilylimidazole (2 ml) was added to the bipyridine group and ethylene group-containing mesoporous organic silica (200 mg) under an argon atmosphere. And the resulting mixture was stirred at 60 ° C. for 12 hours to obtain the following reaction formula (IV):

The reaction product was cooled to 0 ° C. and then added to methanol to stop the reaction. The obtained pale yellow suspension was filtered under reduced pressure using a membrane filter (pore size: 0.5 μm), and the filter cake was dried to obtain a pale yellow powdered bipyridine group and ethylene group-containing mesoporous organic silica (TMS-2, yield). 181 mg, Si-BPy-Si structure content 32.8% by mass (calculated from raw material charge ratio), bipyridine group content 20% by mass (calculated from raw material charge ratio)) were obtained.

When the X-ray diffraction pattern of this mesoporous organic silica TMS-2 was measured in the same manner as in Synthesis Example 1, as shown in FIG. 2A, the mesostructure was regular at 2θ = 1.86 ° (d = 4.75 nm). A derived diffraction peak was observed. Further, when the nitrogen adsorption / desorption isotherm of the mesoporous organic silica TMS-2 was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 2B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, it was confirmed that the mesoporous organic silica TMS-2 has regular mesopores. The characteristics of this mesoporous organic silica TMS-2 were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 1081 m ² / g, the central pore diameter was 27.0 mm, and the pore volume was 0.75 cm ³ / g.

(Synthesis Example 3)
<Synthesis of bipyridine group-supported mesoporous silica>
Under an argon atmosphere, mesoporous silica (FSM-16,500 mg) was dispersed in toluene (20 ml), and 5- (4-triisopropoxysilylbutyl) -5′-methyl-2,2′-bipyridine was dispersed in this dispersion. (BPy-C4-Si, 300 mg, 0.53 mmol) was added. Trifluoroacetic acid (50 μl) was added dropwise to the resulting suspension, followed by stirring for 1 day while refluxing, and the following reaction formula (V):

The reaction represented by The obtained suspension was filtered under reduced pressure using a membrane filter (pore size 0.5 μm), and the filter cake was washed with toluene and methanol and then dried under reduced pressure to obtain bipyridine group-supported mesoporous silica (yield 620 mg). . In order to protect the silanol groups remaining on the outer surface and pore surface of this bipyridine group-supported mesoporous silica, N-trimethylsilylimidazole (3 ml) was added to the bipyridine group-supported mesoporous silica (620 mg) under an argon atmosphere. The resulting mixture was stirred at 60 ° C. for 12 hours, and the following reaction formula (VI):

The reaction product was cooled to 0 ° C. and then added to methanol to stop the reaction. The resulting orange suspension was filtered under reduced pressure using a membrane filter (pore size 0.5 μm), and the filter cake was dried to give a light yellow powder of bipyridine group-supported mesoporous silica (TMS-3, yield 626 mg, BPy-C4). -Si structure content 20 mass% (calculated from the increase in mass) and bipyridine group content 0.433 mmol / g (calculated from the increase in mass)) were obtained.

When the X-ray diffraction pattern of this mesoporous silica TMS-3 was measured in the same manner as in Synthesis Example 1, it was derived from a regular mesostructure at 2θ = 2.28 ° (d = 3.87 nm) as shown in FIG. 3A. A diffraction peak was observed. Further, when the nitrogen adsorption / desorption isotherm of the mesoporous silica TMS-3 was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 3B. Therefore, it was confirmed from the X-ray diffraction pattern and nitrogen adsorption / desorption isotherm that the mesoporous silica TMS-3 has regular mesopores. The characteristics of this mesoporous silica TMS-3 were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 647 m ² / g, the center pore diameter was 22.2 mm, and the pore volume was 0.39 cm ³ / g. Met.

(Synthesis Example 4)
<Synthesis of bipyridine group-supported nonporous silica>
Under an argon atmosphere, amorphous silica gel (silica, 1.0 g) was dispersed in toluene (20 ml), and 5- (4-triisopropoxysilylbutyl) -5′-methyl-2,2 ′ was added to the dispersion. -Bipyridine (185 mg, 0.43 mmol) was added. Trifluoroacetic acid (50 μl) was added dropwise to the resulting suspension, followed by stirring for 1 day while refluxing, and the following reaction formula (VII):

The reaction represented by The obtained suspension was filtered with a membrane filter (pore size 0.5 μm).
Then, the filter cake was washed with toluene and methanol, and then dried under reduced pressure to obtain pyridine group-supported nonporous silica (yield 1.1 g). In order to protect silanol groups remaining on the outer surface and pore surface of the bipyridine group-supported nonporous silica, N-trimethylsilylimidazole (4 ml) was added to the bipyridine group-supported nonporous silica (1100 mg) under an argon atmosphere. And the resulting mixture was stirred at 60 ° C. for 12 hours to obtain the following reaction formula (VIII):

The reaction product was cooled to 0 ° C. and then added to methanol to stop the reaction. The obtained orange suspension was filtered under reduced pressure using a membrane filter (pore size 0.5 μm), and the filter cake was dried to give a light orange powder of bipyridine group-supported nonporous silica (TMS-4, yield 1.10 g, A BPy-C4-Si structure content of 9% by mass (calculated from the mass increase) and a bipyridine group content of 0.328 mmol / g (calculated from the mass increase)) were obtained.

When the X-ray diffraction pattern of this nonporous silica TMS-4 was measured in the same manner as in Synthesis Example 1, it was derived from a diffraction peak derived from a regular mesostructure and a layered arrangement structure of bipyridine groups as shown in FIG. 4A. None of the diffraction peaks were observed. Further, when the nitrogen adsorption / desorption isotherm of the nonporous silica TMS-4 was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 4B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, it was found that the nonporous silica TMS-4 does not have regular mesopores. When the characteristics of this nonporous silica TMS-4 were calculated in the same manner as in Synthesis Example 1, the specific surface area was 443 m ² / g, and the pore volume was below the lower limit of measurement.

(Synthesis Example 5)
<Synthesis of iridium-containing mesoporous organosilica>
Under an argon atmosphere, the bipyridine group-containing mesoporous organic silica TMS-1 (258 mg, 1.00 mmol) obtained in Synthesis Example 1 and di-μ-methoxybis (1,5-cyclooctadiene) diiridium (I) [Ir ( OMe) (cod)] ₂ (16.6 mg, 0.025 mmol (0.050 mmol in terms of Ir atom)) was added, and dehydrated benzene (16.6 ml, 187 mmol) was added to the resulting mixture, and then at room temperature. After stirring for 12 hours, the following reaction formula (IX):

The reaction represented by Diethyl ether was added to the obtained suspension, and solid-liquid separation was performed by vacuum filtration using a membrane filter (pore size: 0.5 μm) (solid component yield: 270 mg).

The X-ray diffraction pattern of this solid component was measured in the same manner as in Synthesis Example 1. As shown in FIG. 5A, a diffraction peak derived from a regular mesostructure at 2θ = 1.80 ° (d = 4.90 nm). Was observed. Further, diffraction derived from a layered arrangement structure of bipyridine groups at 2θ = 11.6 ° (d = 0.76 nm), 15.2 ° (d = 0.58 nm), and 23.0 ° (d = 0.39 nm). A peak was observed. On the other hand, since a diffraction peak of 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was not observed, the iridium species formed a complex with the bipyridine group in the mesoporous organic silica TMS-1. Conceivable. Further, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 5B. Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, the solid component is iridium-containing mesoporous organic silica Ir-TMS-1 in which the bipyridine group in the mesoporous organic silica TMS-1 is coordinated to iridium, It was confirmed that it has typical mesopores. The characteristics of this iridium-containing mesoporous organic silica Ir-TMS-1 were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 560 m ² / g, the center pore diameter was 21.8 mm, and the pore volume was 0. It was .13 cm ³ / g.

Example 1
Under an argon atmosphere, the bipyridine group-containing mesoporous organic silica TMS-1 (25.8 mg, 0.10 mmol) obtained in Synthesis Example 1 and di-μ-methoxybis (1,5-cyclooctadiene) diiridium (I) [ Ir (OMe) (cod)] ₂ (1.66 mg, 2.5 μmol (5.00 μmol in terms of Ir atom)) and bis (pinacolato) diboron (84.6 mg, 0.333 mmol) were mixed, and the resulting mixture After adding dehydrated benzene (1.76 ml, 19.8 mmol) to the mixture, the mixture was stirred at 80 ° C. for 12 hours, and the following reaction formula (X):

The boronation reaction of benzene represented by Diethyl ether was added to the obtained suspension, and solid-liquid separation was performed by vacuum filtration using a membrane filter (pore size 0.5 μm).

Diethyl ether in the obtained liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 128 mg, yield 94%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.35 (s, 12H), 7.37 (t, J = 7.4 Hz, 2H), 7.46 (t, J = 7.3 Hz, 1H), 7.81 (d, J = 7.3 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.87, 83.75, 127.69, 131.23, 134.72.

  On the other hand, when the X-ray diffraction pattern of the collected solid component was measured in the same manner as in Synthesis Example 1, a diffraction peak at 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was observed as shown in FIG. 6A. There wasn't. From this, it is considered that the solid component recovered after the boronation reaction is iridium-containing mesoporous organic silica Ir-TMS-1 in which the bipyridine group in the mesoporous organic silica TMS-1 is coordinated to iridium.

Further, as shown in FIG. 6A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.80 ° (d = 4.90 nm), and 2θ = 11.6 ° (d = 0.76 nm). ), 15.2 ° (d = 0.58 nm), and 23.0 ° (d = 0.39 nm), a diffraction peak derived from a layered arrangement structure of bipyridine groups was observed. Furthermore, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 6B. From these results, it was confirmed that the iridium-containing mesoporous organic silica Ir-TMS-1 recovered after the boronation reaction has regular mesopores, and even after the boronation reaction, the mesoporous organic silica It was found that the regular mesopore structure of TMS-1 was maintained. The properties of the iridium-containing mesoporous organic silica Ir-TMS-1 were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 482 m ² / g, the central pore diameter was 21.4 mm, and the pore volume was 0 It was .14 cm ³ / g.

(Example 2)
Except that pinacol borane (95.6 μl, 0.666 mmol) was used in place of bis (pinacolato) diboron, the same reaction formula (XI) as in Example 1 was used.

The boronation reaction of benzene represented by The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 127 mg, yield 94%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

  On the other hand, when the X-ray diffraction pattern of the collected solid component was measured in the same manner as in Synthesis Example 1, a diffraction peak at 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was observed as shown in FIG. 7A. There wasn't. From this, it is considered that the solid component recovered after the boronation reaction is iridium-containing mesoporous organic silica Ir-TMS-1 in which the bipyridine group in the mesoporous organic silica TMS-1 is coordinated to iridium.

Further, as shown in FIG. 7A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.80 ° (d = 4.90 nm), and 2θ = 11.6 ° (d = 0.76 nm). ), 15.2 ° (d = 0.58 nm), and 23.0 ° (d = 0.39 nm), a diffraction peak derived from a layered arrangement structure of bipyridine groups was observed. Furthermore, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 7B. From these results, it was confirmed that the iridium-containing mesoporous organic silica Ir-TMS-1 recovered after the boronation reaction has regular mesopores, and even after the boronation reaction, the mesoporous organic silica It was found that the regular mesopore structure of TMS-1 was maintained. The characteristics of this iridium-containing mesoporous organic silica Ir-TMS-1 were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 464 m ² / g, the central pore diameter was 20.7 mm, and the pore volume was 0. It was .13 cm ³ / g.

(Example 3)
Instead of the mesoporous organic silica TMS-1 and di-μ-methoxybis (1,5-cyclooctadiene) diiridium (I), the iridium-containing mesoporous organic silica Ir-TMS-1 (27. 5 mg, 5.00 μmol in terms of Ir atom) was used as a solid catalyst in the same manner as in Example 1, but the following reaction formula (XII):

The boronation reaction of benzene represented by The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 126 mg, yield 92%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

  On the other hand, when the X-ray diffraction pattern of the collected solid component was measured in the same manner as in Synthesis Example 1, a diffraction peak at 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was observed as shown in FIG. 8A. There wasn't. From this, it is considered that the solid component recovered after the boronation reaction is iridium-containing mesoporous organic silica Ir-TMS-1 in which the bipyridine group in the mesoporous organic silica TMS-1 is coordinated to iridium. Later, it is presumed that the bipyridine group in the mesoporous organic silica TMS-1 is coordinated to iridium.

Further, as shown in FIG. 8A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.80 ° (d = 4.90 nm), and 2θ = 11.6 ° (d = 0.76 nm). , 15.2 ° (d = 0.58 nm), 23.0 ° (d = 0.39 nm), a diffraction peak derived from a layered structure of bipyridine groups was observed. Furthermore, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 8B. From these results, it was confirmed that the iridium-containing mesoporous organosilica Ir-TMS-1 recovered after the boronation reaction has regular mesopores. It was found that the pore structure was maintained. When the characteristics of the recovered iridium-containing mesoporous organic silica Ir-TMS-1 were calculated in the same manner as in Synthesis Example 1, the specific surface area was 524 m ² / g, the central pore diameter was 20.8 mm, and the pore volume Was 0.10 cm ³ / g.

  As shown in the above results, in Example 1 and Example 3, the solid components recovered after the boronation reaction both have regular mesopores, and the mesoporous organic silica TMS-1 contains Since the bipyridine group is iridium-containing mesoporous organic silica Ir-TMS-1 coordinated to iridium, and the yield of phenylboronic acid pinacol ester is comparable, the mesoporous organic silica according to the present invention and the periodic table Even when mixed with a Group 9 transition metal compound (Example 1), iridium-containing mesoporous organic silica in which the bipyridine group in the mesoporous organic silica is coordinated to iridium is formed, and the same as in Example 3 Furthermore, the iridium-containing mesoporous organosilica acts as a solid catalyst, thereby It is considered a hydrogenation reaction has progressed.

Example 4
The iridium-containing mesoporous organic silica Ir-TMS-1 (83.) recovered in Example 1 instead of the mesoporous organic silica TMS-1 and di-μ-methoxybis (1,5-cyclooctadiene) diiridium (I). 4 mg, 0.015 mmol in terms of Ir atom) was used as a solid catalyst, the amount of bis (pinacolato) diboron was changed to 235 mg (1.00 mmol), and the amount of dehydrated benzene was changed to 5.33 ml (60 mmol) In the same manner as in Example 1, a benzene boronation reaction represented by the formula (X) was carried out (this is the first reuse). The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 369 mg, yield 91%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

  On the other hand, the recovered solid component was repeatedly used as a solid catalyst for the boration reaction of benzene under the conditions described above after drying. The yields of phenylboronic acid pinacol ester in the second and third reuses were 90% and 86%, respectively. In addition, the yield of phenylboronic acid pinacol ester in the fourth reuse was 23%, but in the fifth reuse, the reaction temperature was changed to 120 ° C. and the reaction time was changed to 48 hours. The yield of ester was 50%.

  Further, when the X-ray diffraction pattern and nitrogen adsorption / desorption isotherm of the solid component recovered after the completion of each reaction were determined in the same manner as in Synthesis Example 1, as shown in FIGS. 9A to 9C, in the reuse up to the third time. It was confirmed that the bipyridine group in the mesoporous organic silica TMS-1 was coordinated to iridium and the regular mesopore structure was maintained.

(Example 5)
Instead of the mesoporous organic silica TMS-1, the bipyridine group and ethylene group-containing mesoporous organic silica TMS-2 (39.3 mg, 0.05 mmol) obtained in Synthesis Example 2 was used, and di-μ-methoxybis (1, 5-cyclooctadiene) diiridium (I) [Ir (OMe) (cod)] The amount of ₂ is 0.835 mg (1.25 μmol (2.50 μmol in terms of Ir atom)), and the amount of bis (pinacolato) diboron. Was changed to 42.3 mg (0.167 mmol) and the amount of dehydrated benzene was changed to 0.88 ml (9.9 mmol), in the same manner as in Example 1, the following reaction formula (XIII):

The boronation reaction of benzene represented by The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 55 mg, yield 81%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

  On the other hand, when the X-ray diffraction pattern of the recovered solid component was measured in the same manner as in Synthesis Example 1, a diffraction peak at 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was observed as shown in FIG. 10A. There wasn't. From this, it is considered that the solid component recovered after the boronation reaction is iridium-containing mesoporous organic silica in which the bipyridine group in the mesoporous organic silica TMS-2 is coordinated to iridium.

In addition, as shown in FIG. 10A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.92 ° (d = 4.60 nm). Furthermore, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 10B. From these results, it was confirmed that the iridium-containing mesoporous organic silica recovered after the boronation reaction has regular mesopores, and even after the boronation reaction, the rule of the mesoporous organic silica TMS-2 is confirmed. It was found that a typical mesopore structure was maintained. The properties of this iridium-containing mesoporous organic silica were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 717 m ² / g, the central pore diameter was 27.0 mm, and the pore volume was 0.41 cm ³ / g. Met.

  From the above results, even when mesoporous organic silica TMS-2 containing a bipyridine group and an ethylene group as an organic group was used (Example 5), mesoporous organic silica TMS-1 containing only a bipyridine group as an organic group was used. When used (Example 1), the iridium-containing mesoporous organic silica in which the bipyridine group in the mesoporous organic silica TMS-2 is coordinated to iridium is formed, and this iridium-containing mesoporous organic silica acts as a solid catalyst. Therefore, it is considered that the boronation reaction of benzene has progressed.

( Comparative Example 1 )
Instead of the mesoporous organic silica TMS-1, the bipyridine group-supported mesoporous silica TMS-3 (70.0 mg, 0.05 mmol) obtained in Synthesis Example 3 was used, and di-μ-methoxybis (1,5-cycloocta) was used. The amount of diene) diiridium (I) [Ir (OMe) (cod)] ₂ is 0.835 mg (1.25 μmol (2.50 μmol in terms of Ir atom)), and the amount of bis (pinacolato) diboron is 42.3 mg. (0.167 mmol), except that the amount of dehydrated benzene was changed to 0.88 ml (9.9 mmol), in the same manner as in Example 1, the following reaction formula (XIV):

The boronation reaction of benzene represented by The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 42 mg, yield 63%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

  On the other hand, when the X-ray diffraction pattern of the collected solid component was measured in the same manner as in Synthesis Example 1, a diffraction peak at 2θ = 40.6 ° derived from zero-valent Ir nanoparticles was observed as shown in FIG. 11A. There wasn't. From this, it is considered that the solid component recovered after the boronation reaction is iridium-containing mesoporous organic silica in which the bipyridine group in the mesoporous silica TMS-3 is coordinated to iridium.

In addition, as shown in FIG. 11A, a diffraction peak derived from a regular mesostructure was observed at 2θ = 2.28 ° (d = 3.87 nm). Furthermore, when the nitrogen adsorption / desorption isotherm of the solid component was determined in the same manner as in Synthesis Example 1, it was IV type as shown in FIG. 11B. From these results, it was confirmed that the iridium-containing mesoporous organic silica recovered after the boronation reaction has regular mesopores, and even after the boronation reaction, the regularity of the mesoporous silica TMS-3 was confirmed. It was found that a good mesopore structure was maintained. The properties of the iridium-containing mesoporous organic silica were calculated in the same manner as in Synthesis Example 1. As a result, the specific surface area was 723 m ² / g, the center pore diameter was 21.0 mm, and the pore volume was 0.28 cm ³ / g. Met.

From the above results, even when mesoporous silica TMS-3 carrying a bipyridine group was used ( Comparative Example 1 ), when mesoporous organic silica TMS-1 containing a bipyridine group in the skeleton was used (Example 1) In the same manner as above, iridium-containing mesoporous organic silica in which the bipyridine group in the mesoporous organic silica TMS-3 is coordinated to iridium is formed, and this iridium-containing mesoporous organic silica acts as a solid catalyst. Is considered to have progressed.

(Comparative Example 2 )
In the same manner as in Example 1 except that 2,2′-bipyridine (0.78 mg, 5.00 μmol) was used in place of the mesoporous organic silica TMS-1 and the reaction time was changed to 24 hours, the following reaction formula ( XV):

The boronation reaction of benzene represented by Unreacted substances in the obtained solution were distilled off under reduced pressure to obtain a liquid crude product (yield 108 mg, yield 80%). This crude product contained aggregates of iridium species generated during the boration reaction.

(Comparative Example 3 )
Instead of the mesoporous organic silica TMS-1, the bipyridine group-supported nonporous silica TMS-4 (152.4 mg, 0.05 mmol) obtained in Synthesis Example 4 was used, and di-μ-methoxybis (1,5-cyclohexane) was used. The amount of octadiene) diiridium (I) [Ir (OMe) (cod)] ₂ is 0.835 mg (1.25 μmol (2.50 μmol in terms of Ir atom)), and the amount of bis (pinacolato) diboron is 42. Except that the amount of dehydrated benzene was changed to 3 mg (0.167 mmol) and 0.88 ml (9.9 mmol), the same reaction formula (XVI) as in Example 1 was obtained.

The boronation reaction of benzene represented by The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a colorless and transparent liquid (yield 22.4 mg, yield 33%). This colorless and transparent liquid was identified by ¹ H-NMR measurement and ¹³ C-NMR measurement, and confirmed to be phenylboronic acid pinacol ester.

As is clear from the above results, when mesoporous organic silica TMS-1 or TMS-2 containing a bipyridine group in the skeleton is used (Examples 1 and 5 ), the nonporous silica TMS carrying the bipyridine group is used. As compared with the case where -4 was used (Comparative Example 2 ), it was found that the yield of phenylboronic acid pinacol ester was increased and the catalytic activity of the iridium complex was improved.

(Comparative Example 4 )
Angew. Chem. Int. Ed. 2011, No. 50, pages 11667-11671, the following formula (XVII):

A phenylpyridine group-containing mesoporous organic silica TMS-5 containing a repeating unit represented by the following formula was prepared. This mesoporous organosilica TMS-5 (25.7 mg, 0.10 mmol) was used in place of the mesoporous organosilica TMS-1, and the reaction time was changed to 24 hours. A boronation reaction was attempted. The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a liquid crude product. When this crude product was identified by ¹ H-NMR measurement, the crude product contained no benzene borate, and almost the entire amount of bis (pinacolato) diboron was recovered (recovery rate 99%).

(Comparative Example 5 )
According to Example 2 described in JP 2010-116512 A, the following formula (XVIII):

A pyridine group-containing mesoporous organic silica TMS-6 containing a repeating unit represented by the formula: This mesoporous organosilica TMS-6 (23.3 mg, 0.10 mmol) was used in place of the mesoporous organosilica TMS-1, and the reaction time was changed to 24 hours. A boronation reaction was attempted. The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component.

Diethyl ether in the liquid component was distilled off under reduced pressure to obtain a liquid crude product. When this crude product was identified by ¹ H-NMR measurement, the crude product contained no benzene borate, and almost the entire amount of bis (pinacolato) diboron was recovered (recovery rate 99%).

As is clear from the above results, it was found that when mesoporous organic silica TMS-5 or TMS-6 containing a pyridine group was used (Comparative Examples 4 to 5 ), the boration reaction of benzene did not proceed. .

(Example 7)
In the same manner as in Example 3 except that dehydrated toluene (2.10 ml, 19.8 mmol) was used instead of dehydrated benzene, the following reaction formula (XIX):

The boron boride reaction represented by these was performed. The resulting suspension was treated in the same manner as in Example 1 to obtain a liquid component and a solid component. A membrane filter having a pore diameter of 0.20 μm was used.

Diethyl ether in the liquid component was distilled off under reduced pressure, and the residue was further purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to give a colorless transparent liquid (yield 123.5 mg, yield 85). %). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) toluene and a mixture of p-isomer: m-isomer = 37: 63 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.34 (s, 12H), 2.35 (s, 3H), 7.25-7.27 (m, 2H), 7. 60 (t, J = 4.4 Hz, 1H), 7.63 (s, 1H), (p-isomer) 1.34 (s, 12H), 2.36 (s, 3H), 7.18 (d , J = 7.6 Hz, 2H), 7.70 (d, J = 7.6 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (m-isomer) 21.27, 24.85, 83.71, 127.66, 131.73, 132.01, 135.29, 137.10, ( p-isomer) 21.73, 24.85, 83.60, 128.49, 134.76, 141.37.
ESI-HRMS m / z calcd. _{for C 13 H 23 BNO 2 (} M + NH 4 +): 236.1819; found: 236.1819.

(Example 8)
In the same manner as in Example 7 except that dehydrated anisole (2.15 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XX):

The anisole boronation reaction represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 137.2 mg, yield 88%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) anisole and a mixture of p-isomer: m-isomer = 37: 63 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.34 (s, 12H), 3.83 (s, 3H), 7.00 (dd, J = 2.8, 8.4 Hz) , 1H), 7.29 (t, J = 8.0 Hz, 1H), 7.32 (d, J = 2.8 Hz, 1H), 7.40 (d, J = 7.2 Hz, 1H), ( p-isomer) 1.33 (s, 12H), 3.83 (s, 3H), 6.88 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H) ).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (m-isomer) 24.85, 55.23, 83.80, 117.90, 118.61, 127.14, 128.91, 158.97, ( p-isomer) 24.85, 55.08, 83.53, 113.27, 136.47, 162.08.
ESI-HRMS m / z calcd. _{for C 13 H 23 BNO 3 (} M + NH 4 +): 252.1768; found: 252.1768.

Example 9
In the same manner as in Example 7 except that dehydrated methyl benzoate (2.70 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XXI):

Boronation reaction of methyl benzoate represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 198.4 mg, yield 88%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) methyl benzoate and a mixture of p-isomer: m-isomer = 44: 56 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.36 (s, 12H), 3.91 (s, 3H), 7.44 (t, J = 8.0 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.46 (s, 1H), (p-isomer) 1.36 (s, 12H), 3.92 (s, 3H), 7.86 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (p-isomer) 24.83, 52.10, 84.15, 128.52, 132.23, 134.59, 167.10, (m-isomer) 24.83, 52.00, 84.06, 127.74, 129.47, 135.76, 139.09, 167.07.
ESI-HRMS m / z calcd. _{for C 14 H 23 BNO 4 (} M + NH 4 +): 280.1717; found: 280.1719.

(Example 10)
Except for using dehydrated chlorobenzene (2.02 ml, 19.8 mmol) instead of dehydrated toluene, the same reaction formula (XXII) as in Example 7 was used:

The boronation reaction of chlorobenzene represented by this was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 147.7 mg, yield 93%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) chlorobenzene and a mixture of p-isomer: m-isomer = 34: 66 positional isomers. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (m-isomer) 1.34 (s, 12H), 7.29 (t, J = 8.0 Hz, 1H), 7.41 (dd, J = 8.8 Hz, 2.4 Hz, 1H), 7.66 (d, J = 7.2 Hz, 1H), 7.77 (d, J = 2.4 Hz, 1H), (p-isomer) 1.33. (S, 12H), 7.33 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (m-isomer) 24.84, 84.11, 129.15, 131.22, 132.61, 134.52, 137.21, (p- isomer) 24.84, 84.00, 127.96, 136.09, 137.48.
ESI-HRMS m / z calcd. _{for C 12 H 20 BClNO 2 (} M + NH 4 +): 256.1276; found: 256.1270.

(Example 11)
In the same manner as in Example 7 except that dehydrated benzotrifluoride (2.43 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XXIII):

Boronation reaction of benzotrifluoride represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 141.4 mg, yield 78%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, ¹⁹ F-NMR measurement and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl) (trifluoromethyl) benzene and a mixture of p-isomer: m-isomer = 32: 68 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (m-isomer) 1.36 (s, 12H), 7.48 (t, J = 7.6 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 8.06 (s, 1H), (p-isomer) 1.36 (s, 12H), 7.61 ( d, J = 8.1 Hz, 2H), 7.91 (d, J = 7.8 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (m-isomer) 24.85, 84.26, 124.29, 127.60, 127.99, 131.32, 137.96, (p- isomer) 24.53, 84.26, 124.15, 124.29, 132.30, 134.96.
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ (m-isomer) -62.93, (p-isomer) -62.51.
ESI-HRMS m / z calcd. _{for C 13 H 20 BF 3 NO} 2 (M + NH 4 +): 250.1539; found: 250.1539.

(Example 12)
Except for using dehydrated o-xylene (2.39 ml, 19.8 mmol) in place of dehydrated toluene, the same reaction formula (XXIV) as in Example 7 was used:

The boronation reaction of o-xylene represented by these was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 139.3 mg, yield 60%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained. 2-yl) -o-xylene was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.34 (s, 12H), 2.27 (s, 3H), 2.28 (s, 3H), 7.14 (d, J = 7.6 Hz, 1H), 7.54 (d, J = 7.6 Hz, 1H), 7.58 (s, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 19.47, 20.00, 24.83, 83.56, 129.13, 132.36, 135.88, 140.12.
ESI-HRMS m / z calcd. _{for C 14 H 25 BNO 2 (} M + NH 4 +): 250.1975; found: 250.1975.

(Example 13)
In the same manner as in Example 7 except that dehydrated 1,2-dichlorobenzene (2.23 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XXV):

Boronation reaction of 1,2-dichlorobenzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 167.2 mg, yield 92%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry (HRMS), and 1,2-dichloro-4- (4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ1.33 (s, 12H), 7.43 (d, J = 8.0 Hz, 1H), 7.59 (dd, J = 1.2 Hz, 8.0 Hz) , 1H), 7.86 (d, J = 1.6 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 25.15, 84.64, 130.29, 132.53, 134.04, 135.77, 136.83.
ESI-HRMS m / z calcd. _{for C 12 H 19 BNCl 2 O} 2 (M + NH 4 +): 290.0883; found: 290.0882.

(Example 14)
In the same manner as in Example 7 except that dehydrated 1,3-dichlorobenzene (2.26 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XXVI):

Boronation reaction of 1,3-dichlorobenzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. The liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 147.2 mg, yield 81%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry (HRMS), and 1,3-dichloro-5- (4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.34 (s, 12H), 7.42 (t, J = 2.0 Hz, 1H), 7.64 (d, J = 2.0 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.83, 84.48, 129.34, 131.04, 132.66, 134.68.
ESI-HRMS m / z calcd. _{for C 12 H 19 BNCl 2 O} 2 (M + NH 4 +): 290.0883; found: 290.0884.

(Example 15)
In the same manner as in Example 7 except that dehydrated 1,3-bis (trifluoromethyl) benzene (3.04 ml, 19.8 mmol) was used instead of dehydrated toluene, the following reaction formula (XXVII):

Boronation reaction of 1,3-bis (trifluoromethyl) benzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 106.4 mg, yield 47%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, ¹⁹ F-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 1,3-bis (trifluoromethyl) -5- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.37 (s, 12H), 7.94 (s, 1H), 8.23 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.86, 84.83, 122.09, 124.66, 124.69, 130.68, 131.02, 134.61.
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-62.76.
ESI-HRMS m / z calcd. _{for C 14 H 19 BNF 6 O} 2 (M + NH 4 +): 358.1410; found: 358.1408.

(Example 16)
Under an argon atmosphere, iridium-containing mesoporous organic silica Ir-TMS-1 obtained in Synthesis Example 5 (27.5 mg, 5.00 μmol in terms of Ir atom) was added to dehydrated benzene (1.76 ml, 19.8 mmol) and pinacol borane ( (85.2 mg, 0.666 mmol) was added, and the mixture was stirred at 80 ° C. for 12 hours to obtain the following reaction formula (XXVIII):

The boronation reaction of benzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 127.8 mg, yield 94%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.35 (s, 12H), 7.37 (t, J = 7.4 Hz, 2H), 7.46 (t, J = 7.3 Hz, 1H), 7.81 (d, J = 7.3 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.87, 83.75, 127.69, 131.23, 134.72.
ESI-HRMS m / z calcd. for C ₁₂ H ₂₁ BNO ₂ (M + NH ₄ ⁺ ): 222.1662; found: 222.1664.

(Example 17)
In the same manner as in Example 16 except that dehydrated toluene (2.10 ml, 19.8 mmol) was used instead of dehydrated benzene, the following reaction formula (XXIX):

The boron boride reaction represented by these was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. The liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 133.6 mg, yield 92%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) toluene and a mixture of p-isomer: m-isomer = 40: 60 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.34 (s, 12H), 2.35 (s, 3H), 7.25-7.27 (m, 2H), 7. 60 (t, J = 4.4 Hz, 1H), 7.63 (s, 1H), (p-isomer) 1.34 (s, 12H), 2.36 (s, 3H), 7.18 (d , J = 7.6 Hz, 2H), 7.70 (d, J = 7.6 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (m-isomer) 21.27, 24.85, 83.71, 127.66, 131.73, 132.01, 135.29, 137.10, ( p-isomer) 21.73, 24.85, 83.60, 128.49, 134.76, 141.37.
ESI-HRMS m / z calcd. _{for C 13 H 23 BNO 2 (} M + NH 4 +): 236.1819; found: 236.1819.

(Example 18)
In the same manner as in Example 16 except that dehydrated anisole (2.15 ml, 19.8 mmol) was used instead of dehydrated benzene, the following reaction formula (XXX):

The anisole boronation reaction represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 135.6 mg, yield 87%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) anisole, and a mixture of p-isomer: m-isomer = 49: 51 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.34 (s, 12H), 3.83 (s, 3H), 7.00 (dd, J = 2.8, 8.4 Hz) , 1H), 7.29 (t, J = 8.0 Hz, 1H), 7.32 (d, J = 2.8 Hz, 1H), 7.40 (d, J = 7.2 Hz, 1H), ( p-isomer) 1.33 (s, 12H), 3.83 (s, 3H), 6.88 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H) ).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (m-isomer) 24.85, 55.23, 83.80, 117.90, 118.61, 127.14, 128.91, 158.97, ( p-isomer) 24.85, 55.08, 83.53, 113.27, 136.47, 162.08.
ESI-HRMS m / z calcd. _{for C 13 H 23 BNO 3 (} M + NH 4 +): 252.1768; found: 252.1768.

(Example 19)
Under an argon atmosphere, iridium-containing mesoporous organic silica Ir-TMS-1 obtained in Synthesis Example 5 (27.5 mg, 5.00 μmol in terms of Ir atom) was added to dehydrated cyclohexane (2.0 ml) and dehydrated methyl benzoate (181 mg, 1.33 mmol) and pinacol borane (85.2 mg, 0.666 mmol) were added, and the mixture was stirred at 80 ° C. for 12 hours to obtain the following reaction formula (XXXI):

Boronation reaction of methyl benzoate represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 150.1 mg, yield 86%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) methyl benzoate and a mixture of p-isomer: m-isomer = 47: 53 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (m-isomer) 1.36 (s, 12H), 3.91 (s, 3H), 7.44 (t, J = 8.0 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.46 (s, 1H), (p-isomer) 1.36 (s, 12H), 3.92 (s, 3H), 7.86 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ (p-isomer) 24.83, 52.10, 84.15, 128.52, 132.23, 134.59, 167.10, (m-isomer) 24.83, 52.00, 84.06, 127.74, 129.47, 135.76, 139.09, 167.07.
ESI-HRMS m / z calcd. _{for C 14 H 23 BNO 4 (} M + NH 4 +): 280.1717; found: 280.1719.

(Example 20)
Except for using dehydrated benzotrifluoride (194 mg, 1.33 mmol) instead of dehydrated methyl benzoate, the same reaction formula (XXXII) as in Example 19 was used.

Boronation reaction of benzotrifluoride represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 166.7 mg, yield 92%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, ¹⁹ F-NMR measurement and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl) (trifluoromethyl) benzene and a mixture of p-isomer: m-isomer = 31: 69 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (m-isomer) 1.36 (s, 12H), 7.48 (t, J = 7.6 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 8.06 (s, 1H), (p-isomer) 1.36 (s, 12H), 7.61 ( d, J = 8.1 Hz, 2H), 7.91 (d, J = 7.8 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (m-isomer) 24.85, 84.26, 124.29, 127.60, 127.99, 131.32, 137.96, (p- isomer) 24.53, 84.26, 124.15, 124.29, 132.30, 134.96.
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ (m-isomer) -62.93, (p-isomer) -62.51.
ESI-HRMS m / z calcd. _{for C 13 H 20 BF 3 NO} 2 (M + NH 4 +): 250.1539; found: 250.1539.

(Example 21)
Except for using dehydrated chlorobenzene (150 mg, 1.33 mmol) in place of dehydrated methyl benzoate, the same reaction formula (XXXIII) as in Example 19 was used.

The boronation reaction of chlorobenzene represented by this was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 154 mg, yield 97%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, and high-resolution mass spectrometry (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. 2-yl) chlorobenzene, and a mixture of p-isomer: m-isomer = 35: 65 positional isomer. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (m-isomer) 1.34 (s, 12H), 7.29 (t, J = 8.0 Hz, 1H), 7.41 (dd, J = 8.8 Hz, 2.4 Hz, 1H), 7.66 (d, J = 7.2 Hz, 1H), 7.77 (d, J = 2.4 Hz, 1H), (p-isomer) 1.33. (S, 12H), 7.33 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (m-isomer) 24.84, 84.11, 129.15, 131.22, 132.61, 134.52, 137.21, (p- isomer) 24.84, 84.00, 127.96, 136.09, 137.48.
ESI-HRMS m / z calcd. _{for C 12 H 20 BClNO 2 (} M + NH 4 +): 256.1276; found: 256.1270.

(Example 22)
In the same manner as in Example 16 except that dehydrated o-xylene (2.39 ml, 19.8 mmol) was used instead of dehydrated benzene, the following reaction formula (XXXIV):

The boronation reaction of o-xylene represented by these was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 105 mg, yield 68%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained. 2-yl) -o-xylene was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.34 (s, 12H), 2.27 (s, 3H), 2.28 (s, 3H), 7.14 (d, J = 7.6 Hz, 1H), 7.54 (d, J = 7.6 Hz, 1H), 7.58 (s, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 19.47, 20.00, 24.83, 83.56, 129.13, 132.36, 135.88, 140.12.
ESI-HRMS m / z calcd. _{for C 14 H 25 BNO 2 (} M + NH 4 +): 250.1975; found: 250.1975.

(Example 23)
Except for using dehydrated 1,2-dichlorobenzene (195.8 mg, 1.33 mmol) instead of dehydrated methyl benzoate, the following reaction formula (XXXV):

Boronation reaction of 1,2-dichlorobenzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 172.7 mg, yield 95%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry (HRMS), and 1,2-dichloro-4- (4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ1.33 (s, 12H), 7.43 (d, J = 8.0 Hz, 1H), 7.59 (dd, J = 1.2 Hz, 8.0 Hz) , 1H), 7.86 (d, J = 1.6 Hz, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 25.15, 84.64, 130.29, 132.53, 134.04, 135.77, 136.83.
ESI-HRMS m / z calcd. _{for C 12 H 19 BNCl 2 O} 2 (M + NH 4 +): 290.0883; found: 290.0882.

(Example 24)
Except that dehydrated 1,3-dichlorobenzene (196 mg, 1.33 mmol) was used in place of dehydrated methyl benzoate, the same reaction formula (XXXVI) as in Example 19 was used.

Boronation reaction of 1,3-dichlorobenzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a colorless and transparent liquid (yield 171 mg, yield 94%). This colorless and transparent liquid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry (HRMS), and 1,3-dichloro-5- (4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.34 (s, 12H), 7.42 (t, J = 2.0 Hz, 1H), 7.64 (d, J = 2.0 Hz, 2H) .
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.83, 84.48, 129.34, 131.04, 132.66, 134.68.
ESI-HRMS m / z calcd. _{for C 12 H 19 BNCl 2 O} 2 (M + NH 4 +): 290.0883; found: 290.0884.

(Example 25)
In the same manner as in Example 19 except that dehydrated 1,3-bis (trifluoromethyl) benzene (285.2 mg, 1.33 mmol) was used instead of dehydrated methyl benzoate, the following reaction formula (XXXVII):

Boronation reaction of 1,3-bis (trifluoromethyl) benzene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 206 mg, yield 91%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement, ¹⁹ F-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 1,3-bis (trifluoromethyl) -5- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.37 (s, 12H), 7.94 (s, 1H), 8.23 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ ): δ 24.86, 84.83, 122.09, 124.66, 124.69, 130.68, 131.02, 134.61.
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-62.76.
ESI-HRMS m / z calcd. _{for C 14 H 19 BNF 6 O} 2 (M + NH 4 +): 358.1410; found: 358.1408.

(Example 26)
Except that dehydrated thiophene (223 mg, 2.66 mmol) was used instead of dehydrated methyl benzoate, the same reaction formula (XXXVIII) as that in Example 19 was obtained.

Boronation reaction of thiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 128.7 mg, yield 92%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. -2-yl) thiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.35 (s, 12 H), 7.19 (dd, J = 3.6 Hz, 4.4 Hz, 1 H), 7.63 (d, J = 4 .8 Hz, 1 H), 7.64 (d, J = 3.6 Hz, 1 H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.76, 84.07, 128.20, 132.34, 137.13.
ESI-HRMS m / z calcd. for C ₁₀ H ₁₉ BNO ₂ S (M + NH ₄ ⁺ ): 228.1224; found: 228.1224.

(Example 27)
Except for using dehydrated methyl 2-furancarboxylate (168 mg, 1.33 mmol) in place of dehydrated methyl benzoate, the same reaction formula (XXXIX) as in Example 19 was used.

Boronation reaction of methyl 2-furancarboxylate represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 156.1 mg, yield 93%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 was identified. -Yl) -2-furancarboxylate, and a mixture of 2-isomer: 3-isomer = 86: 14 positional isomers. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (2-isomer) 1.35 (s, 12H), 3.89 (s, 3H), 7.07 (d, J = 3.6 Hz, 1H) ), 7.19 (d, J = 3.6 Hz, 1H), (3-isomer) 1.32 (s, 12H), 3.89 (s, 3H), 7.37 (s, 1H), 7 .87 (s, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (2-isomer) 24.70, 51.93, 84.70, 117.86, 124.00, 148.29, 159.03, (3- isomer) 24.75, 51.95, 83.91, 121.80, 123.9, 154.01, 159.07.
ESI-HRMS m / z calcd. for C ₁₂ H ₂₁ BNO ₅ (M + NH ₄ ⁺ ): 270.1507; found: 270.1508.

(Example 28)
Except for using dehydrated benzo [b] thiophene (179 mg, 1.33 mmol) in place of dehydrated methyl benzoate, the same reaction formula (XL) as in Example 19 was used.

Boronation reaction of benzo [b] thiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 156.0 mg, yield 90%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. -2-yl) benzo [b] thiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.38 (s, 12H), 7.32-7.39 (m, 2H), 7.83-7.86 (m, 1H), 7. 88 (s, 1H), 7.89-7.91 (m, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.81, 84.42, 122.49, 124.07, 124.34, 125.27, 134.46, 140.39, 143.66.
ESI-HRMS m / z calcd. _{for C 14 H 21 BNO 2 S} (M + NH 4 +): 278.1381; found: 278.1382.

(Example 29)
Under an argon atmosphere, iridium-containing mesoporous organic silica Ir-TMS-1 obtained in Synthesis Example 5 (27.5 mg, 5.00 μmol in terms of Ir atom) and benzofuran (157.4 mg, 1.33) mmol were mixed, After adding dehydrated cyclohexane (2.0 ml) and pinacol borane (85.2 mg, 0.666 mmol) to the resulting mixture, the mixture was stirred at 80 ° C. for 12 hours, and the following reaction formula (XLI):

The boronation reaction of benzofuran represented by this was performed. The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 149.6 mg, yield 92%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2 was identified. -Yl) benzofuran and a mixture of 2-isomer: 3-isomer = 80: 20 positional isomers. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ (2-somer) 1.39 (s, 12H), 7.22 (t, J = 7.2 Hz, 1H), 7.33 (dt, J = 1.2 Hz, 7.2 Hz, 1 H), 7.40 (s, 1 H), 7.56 (d, J = 8.4 Hz, 1 H), 7.62 (d, J = 8.0 Hz, 1 H) , (3-isomer) 1.37 (s, 12H), 7.26-7.29 (m, 2H), 7.91-7.93 (m, 2H), 7.95 (s, 1H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ (2-isomer) 24.77, 84.66, 111.93, 119.51, 121.85, 122.70, 125.90, 127.44 157.46, (3-isomer) 24.87, 83.48, 111.0, 122.84, 122.92, 124.19, 153.5.
ESI-HRMS m / z calcd. _{for C 14 H 21 BNO 3 (} M + NH 4 +): 262.1609; found: 272.1612.

(Example 30)
Except that indole (156 mg, 1.33 mmol) was used instead of benzofuran, the same reaction formula (XLII) as that in Example 29:

The indole boronation reaction represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 150 mg, yield 93%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane was identified. -2-yl) Indole was confirmed. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.37 (s, 12H), 7.09 (t, J = 8.0 Hz, 1H), 7.11 (s, 1H), 7.22 ( t, J = 8.0 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H), 8.55 (brs, 1H) .
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.83, 84.13, 111.24, 113.82, 119.76, 121.58, 123.60, 128.24, 138.17.
ESI-HRMS m / z calcd. for C ₁₄ H ₁₉ BNO ₂ (M + H ⁺ ): 244.1503; found: 244.1507.

(Example 31)
In the same manner as in Example 29 except that 2,6-dichloropyridine (197 mg, 1.33 mmol) was used instead of benzofuran, the following reaction formula (XLIII):

Boronation reaction of 2,6-dichloropyridine represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 7 to obtain a white solid (yield 167.8 mg, yield 92%). As a developing solvent for silica gel column chromatography, a mixed solvent of hexane / acetone (10/1) was used. This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2,6-dichloro-4- (4,4,5,5-tetramethyl-1 , 3,2-dioxaborolan-2-yl) pyridine. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.35 (s, 12H), 7.58 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.82, 85.19, 127.75, 150.37.
ESI-HRMS m / z calcd. for C ₁₁ H ₁₅ BCl ₂ NO ₂ (M + H ⁺ ): 274.0567; found: 274.0569.

(Example 32)
Except for using dehydrated thiophene (18.6 mg, 0.222 mmol) in place of dehydrated methyl benzoate, the same reaction scheme (XLIV) as in Example 19 was used.

Boronation reaction of thiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. Diethyl ether in the liquid component was distilled off under reduced pressure, and the residue was washed with hexane (1 ml) cooled to 0 ° C. and then dried to obtain a white solid (yield 73.8 mg, yield 99%). This white solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2,5-bis (4,4,5,5-tetramethyl-1,3, It was confirmed that it was 2-dioxaborolan-2-yl) thiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.34 (s, 24H), 7.66 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.76, 84.11, 137.64.
ESI-HRMS m / z calcd. _{for C 16 H 27 B 2 O} 4 S (M +): 337.1811; found: 337.1718.

(Example 33)
In the same manner as in Example 29 except that 2,2′-bithiophene (36.9 mg, 0.222 mmol) was used instead of benzofuran, the following reaction formula (XLV):

The boronation reaction of 2,2′-bithiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. The liquid component was treated in the same manner as in Example 32 to obtain a pale yellow solid (yield 91.9 mg, yield 99%). This pale yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 5,5′-bis (4,4,5,5-tetramethyl-1, It was confirmed to be 3,2-dioxaborolan-2-yl) -2,2′-bithiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.35 (s, 24H), 7.28 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H) ).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.76, 84.21, 125.60, 137.95, 143.83.
ESI-HRMS m / z calcd. _{for C 20 H 29 B 2 O} 4 S 2 (M +): 419.1688; found: 419.1698.

(Example 34)
In the same manner as in Example 29 except that 2,2 ′: 5 ′, 2 ″ -terthiophene (55.1 mg, 0.222 mmol) was used instead of benzofuran, the following reaction formula (XLVI):

A boron component reaction of 2,2 ′: 5 ′, 2 ″ -terthiophene represented by the following formula was performed. The resulting suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 32 to obtain a yellow solid (yield 110 mg, yield 99%), which was analyzed by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass. 5,5 ″ -bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -2,2 ′: 5 ′, 2 identified by analytical spectrum measurement (HRMS) It confirmed that it was "-terthiophene. The result is shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.35 (s, 24H), 7.14 (s, 2H), 7.23 (d, J = 3.6 Hz, 2H), 7.52 ( d, J = 3.6 Hz, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.77, 84.22, 124.97, 125.11, 136.63, 137.95, 143.61.
FI-HRMS m / z calcd. _{for C 24 H 31 B 2 O} 4 S 3 (M +): 501.1565; found: 501.1577.

(Example 35)
In the same manner as in Example 29 except that benzo [1,2-b: 4,5-b ′] dithiophene (42.3 mg, 0.222 mmol) was used instead of benzofuran, the following reaction formula (XLVII):

Boronation reaction of benzo [1,2-b: 4,5-b ′] dithiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 32 to obtain a pale yellow solid (yield 97.2 mg, yield 99%). This pale yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2,6-bis (4,4,5,5-tetramethyl-1,3 , 2-dioxaborolan-2-yl) benzo [1,2-b: 4,5-b ′] dithiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.39 (s, 24H), 7.90 (s, 2H), 8.36 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.83, 84.54, 117.52, 133.59, 139.31, 140.56.
ESI-HRMS m / z calcd. for C ₂₂ H ₂₉ B ₂ O ₄ S ₂ (M ⁺ ): 443.1688; found: 443.1696.

(Example 36)
In the same manner as in Example 29 except that 4,8-dihexyloxybenzo [1,2-b: 4,5-b ′] dithiophene (48.9 mg, 0.222 mmol) was used instead of benzofuran, Reaction formula (XLVIII):

Boronation reaction of 4,8-dihexyloxybenzo [1,2-b: 4,5-b ′] dithiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. The liquid component was treated in the same manner as in Example 32 to obtain a pale yellow solid (yield 100 mg, yield 95%). This pale yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2,6-bis (4,4,5,5-tetramethyl-1,3 , 2-dioxaborolan-2-yl) -4,8-dihexyloxybenzo [1,2-b: 4,5-b ′] dithiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 0.93 (t, J = 6.8 Hz, 6H), 1.36 to 1.38 (m, 12H), 1.38 (s, 24H), 1.50-1.55 (m, 4H), 1.84-1.91 (m, 4H), 4.30 (t, J = 6.8 Hz, 4H), 8.01 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 14.10, 22.65, 24.71, 24.81, 25.66, 30.53, 31.70, 73.94, 84.55, 130 .82, 132.98, 133.77, 144.82.
ESI-HRMS m / z calcd. for C ₃₄ H ₅₃ B ₂ O ₆ S ₂ (M ⁺ ): 643.3464; found: 643.3472.

(Example 37)
Except that thieno [3,2-b] thiophene (31.1 mg, 0.222 mmol) was used in place of benzofuran, the same reaction formula (XLIX) as in Example 29 was used.

The boronation reaction of thieno [3,2-b] thiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 32 to obtain a pale yellow solid (yield 86.2 mg, yield 99%). This pale yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high resolution mass spectrometry spectrum measurement (HRMS), and 2,5-bis (4,4,5,5-tetramethyl-1,3 , 2-dioxaborolan-2-yl) thieno [3,2-b] thiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.36 (s, 24H), 7.75 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.79, 84.35, 128.87, 146.61.
ESI-HRMS m / z calcd. for C ₁₈ H ₂₇ B ₂ O ₄ S ₂ (M ⁺ ): 393.1531; found: 393.1539.

(Example 38)
In the same manner as in Example 29 except that dithieno [3,2-b: 2 ′, 3′-d] thiophene (43.6 mg, 0.222 mmol) was used instead of benzofuran, the following reaction formula (L):

Boronation reaction of dithieno [3,2-b: 2 ′, 3′-d] thiophene represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 32 to obtain a pale yellow solid (yield 93.7 mg, yield 89%). This pale yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and 2,6-bis (4,4,5,5-tetramethyl-1,3 , 2-dioxaborolan-2-yl) dithieno [3,2-b: 2 ′, 3′-d] thiophene. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.36 (s, 24H), 7.76 (s, 2H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.78, 84.40, 130.27, 144.74.
ESI-HRMS m / z calcd. _{for C 20 H 27 B 2 O} 4 S 3 (M +): 449.1252; found: 449.1259.

(Example 39)
In the same manner as in Example 29, except that tris [(4- (5-thiophen) -2-yl) phenyl)] amine (72.8 mg, 0.148 mmol) was used instead of benzofuran, the following reaction formula (LI ):

The boronation reaction of tris [(4- (5-thiophen) -2-yl) phenyl)] amine represented by The obtained suspension was treated in the same manner as in Example 7 to obtain a liquid component and a solid component. This liquid component was treated in the same manner as in Example 32 to obtain a yellow solid (yield 126 mg, yield 98%). This yellow solid was identified by ¹ H-NMR measurement, ¹³ C-NMR measurement and high-resolution mass spectrometry spectrum measurement (HRMS), and tris [4- (5- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) thiophen-2-yl) phenyl] amine. The results are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS): δ 1.36 (s, 36H), 7.13 (d, J = 8.8 Hz, 6H), 7.32 (d, J = 3.6 Hz, 3H) ), 7.55 (d, J = 8.8 Hz, 6H), 7.58 (d, J = 3.6 Hz, 3H).
¹³ C-NMR (100 MHz, CDCl ₃ , TMS): δ 24.79, 84.11, 123.85, 124.42, 127.10, 129.13, 138.23, 146.73, 150.92.
ESI-HRMS m / z calcd. _{for C 48 H 55 B 3 NO} 6 S 3 (M +): 870.3465; found: 870.3484.

  As is clear from the above results, it was confirmed that the solid catalyst of the present invention is useful for the boronation reaction of various aromatic compounds.

  As described above, according to the present invention, it is possible to obtain a solid catalyst that contains a transition metal atom of Group 9 of the periodic table such as an iridium atom and has excellent catalytic activity.

  Therefore, since the solid catalyst of the present invention exhibits excellent catalytic activity in the boronation reaction of aromatic compounds such as benzene, it is useful as a C—H bond activation catalyst.

Claims (3)

Following formula (1):
[In the formula (1), M represents a transition metal atom of Group 9 of the periodic table, L ¹ and L ² represent the same or different ligands, and at least one group of R ^{1 to} R ⁸ is The following formula (2):
(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. An organic group or a single bond; R ^a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group; R ^b represents a hydrogen atom or a silyl group; k is 1 or 2; Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are present in the group represented by the formula (2). Independent, * is a binding site with an adjacent structure)
The remaining groups of R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, or an alkyl group, aryl group, alkoxy group, phenoxy group, acetyl group, benzoyl group, amino group A monovalent or divalent organic group selected from the group consisting of amide group, imide group, nitro group and cyano group]
Carbon-hydrogen, comprising a transition metal-containing mesoporous organic silica having a structure represented by formula (1), wherein the structure represented by the formula (1) is contained in the skeleton of the transition metal-containing mesoporous organic silica. A solid catalyst used in a boronation reaction involving bond cleavage . That at least one group of R ^{1 to} R ⁴ and at least one group of R ^{5 to} R ^{8 in} the formula (1) are each independently a group represented by the formula (2). The solid catalyst according to claim 1 , wherein Solid catalyst according to claim 1 or of 2 M the formula (1) is characterized in that an iridium atom.