JP5008063B2 - Diphosphine core type amphiphilic dendrimer, process for producing the same, bidentate phosphine ligand and palladium-containing complex compound having a coordination structure thereof - Google Patents

Description

  The present invention relates to a novel diphosphine core type amphiphilic dendrimer, a method for producing the same, a bidentate phosphine ligand comprising the dendrimer, and a palladium-containing complex compound having a coordination structure thereof.

  A dendrimer has a molecular structure that branches like a tree from the central core, and consists of a central part called the core, a branched repeating part called the dendron, and a terminal group, which can control the molecular structure and molecular size highly. It is a possible polymer compound. In recent years, attempts have been made to use it as a functional polymer by introducing functional groups into various sites of the dendrimer, focusing on this unique structure (see Non-Patent Document 1).

  One of them is to provide a dendrimer with a catalytic function, and many dendrimer-fixed catalysts have been developed so far, most of which have the catalyst immobilized on the outermost shell of the dendrimer molecule and the catalyst immobilized on the core. (See Non-Patent Documents 2 and 3).

  For example, as a typical dendrimer-immobilized organometallic catalyst, a dendrimer-fixed nickel complex catalyst using a diamine introduced at the end of the dendrimer as a bidentate ligand (see Non-Patent Document 4), introduced into the core of a lipophilic dendrimer And a dendrimer-fixed platinum phosphine complex catalyst having a phosphine skeleton or diphosphine skeleton as a ligand (see Non-Patent Document 5).

  In addition, the dendrimer-fixed organometallic complex catalyst is nano-sized, so it can be applied to liquid phase membrane reactors (membrane reactors) to enable continuous reaction by recycling the dendrimer-fixed catalyst (non- (See Patent Documents 6 and 7). In this case, particularly when the metal catalyst is fixed to bidentate, the elimination of the metal active species is suppressed because of bidentity, and thus efficient recycling of the complex catalyst is achieved.

“Dendrimers and Dendrons”, 2001, p. 51 (WILEY-VCH) “The Journal of Synthetic Organic Chemistry”, 2000, Vol. 58, p. 988 “Chemical Industry”, 2001, Vol. 52, p. 933 “Nature”, 1994, 372, p. 659 “Organometallics”, 2001, Vol. 20, p. 5342 “Journal of the American Chemical Society (J. Am. Chem. Soc.)”, 1996, Vol. 118, p. 11111 “Journal of Catalyst” (J. Cat.), 1999, Vol. 183, p. 163

  Under such circumstances, the object of the present invention is to have a hydrophilic group at the terminal portion of the dendrimer, which is useful as a bidentate phosphine ligand as a raw material for an organometallic complex catalyst for organic synthesis in water. Another object of the present invention is to provide a diphosphine core type amphiphilic dendrimer having a diphosphine skeleton in the core.

  As a result of intensive studies on the diphosphine core-type amphiphilic dendrimer having a hydrophilic group at the terminal portion of the dendrimer, the present inventors have reduced the corresponding amphiphilic dendrimer-fixed diphosphine oxide in a solvent. A novel diphosphine core type amphiphilic dendrimer can be easily obtained by hydrolysis of an ester group at the end of a diphosphine core type dendrimer, and the diphosphine core type amphiphilic dendrimer can be used as a bidentate ligand; The amphiphilic dendrimer-fixed palladium phosphine complex prepared using this as a bidentate ligand efficiently promotes organic reactions activated by palladium phosphine complex catalysts in water. Finding usefulness as a complex catalyst This has led to the completion of the present invention based.

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｘは水素原子、カルボキシル基、リチウムカルボキシレート基、ナトリウムカルボキシレート基又はカリウムカルボキシレート基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合はＸは水素原子以外の前述した官能基である）
で表される基である］
で表されるデンドリマーであることを特徴とするジホスフィンコア型両親媒性デンドリマー。
〈２〉 一般式（ＩＩＩ）

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇ′は一般式（ＩＶ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｋは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表される基である］
で表されるジホスフィンオキシドコア型デンドリマーを、溶媒中で還元することを特徴とする一般式（Ｖ）

（式中、Ｕ、Ｇ′は上記のとおりである）
で表されるジホスフィンコア型両親媒性デンドリマーの製造方法。
〈３〉 一般式（ＶＩ）

［Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇ″は一般式（ＶＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｒ^５は炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｍは０以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表される基である］
で表されるジホスフィンコア型デンドリマーを、塩基を用いて加水分解した後酸と反応させ、場合によりさらに水酸化リチウム、水酸化ナトリウム又は水酸化カリウムと反応させることを特徴とする一般式（ＶＩＩＩ）

［式中、Ｕは上記のとおりであり、Ｇ^＊は一般式（ＩＸ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｐ、ｑ、ｒ、ｓ、ｔ、Ｙ、Ｚ、ｎ、ｄ、ｅ及びfは上記のとおりであり、Ｍは水素原子、リチウム原子、ナトリウム原子又はカリウム原子を示す）
で表される基である］
で表されるジホスフィンコア型両親媒性デンドリマーの製造方法。
〈４〉 前記〈１〉記載のジホスフィンコア型両親媒性デンドリマーからなる二座ホスフィン配位子。
〈５〉 前記〈４〉記載の二座ホスフィン配位子を含む配位構造を有する一般式（Ｘ）

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｘは水素原子、カルボキシル基、リチウムカルボキシレート基、ナトリウムカルボキシレート基又はカリウムカルボキシレート基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合Ｘは水素原子以外の前述した官能基である）
で表される基、Ｌ^１はハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、硝酸イオン又は酢酸イオンを示す］
又は一般式（ＸＩ）

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｘは水素原子、カルボキシル基、リチウムカルボキシレート基、ナトリウムカルボキシレート基又はカリウムカルボキシレート基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合はＸは水素原子以外の前述した官能基である）
で表される基、Ｌ^２及びＬ^３はそれぞれ異なって、ハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、硝酸イオン、酢酸イオン又はアリルアニオンを示す］
で表される両親媒性デンドリマー固定型パラジウム（ＩＩ）ジホスフィン錯体。
〈６〉上記〈５〉に記載の含パラジウム錯体化合物の中から選ばれた少なくとも１種からなる水中での炭素−炭素結合生成反応用触媒。 That is, according to this application, the following invention is provided.
<1> General formula (I)

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G is a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
Is a group represented by
A diphosphine core type amphiphilic dendrimer represented by the formula:
<2> General formula (III)

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G ′ is a compound represented by the general formula (IV)

Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, p, q , R, s, and t are each 0 or 1, n is an integer of 1 or more, k is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
Is a group represented by
A diphosphine oxide core-type dendrimer represented by the general formula (V):

(Where U and G 'are as described above)
The manufacturing method of the diphosphine core type amphiphilic dendrimer represented by these.
<3> General formula (VI)

[U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, G ″ is a general formula (VII)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, R ⁵ is a hydrocarbon group, Y and Z are 2 consisting of O, S, SO, SO ₂ , an amide group or a carbonyl group. Valent linking group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, m is an integer of 0 or more, at least two of d, e and f are 1, and the rest are 0 )
Is a group represented by
The diphosphine core-type dendrimer represented by the general formula (VIII) is characterized by being hydrolyzed with a base and then reacted with an acid, and optionally further reacted with lithium hydroxide, sodium hydroxide or potassium hydroxide.

[Wherein U is as defined above, and G ^* is the general formula (IX)

(Wherein R ¹ , R ² , R ³ , R ⁴ , p, q, r, s, t, Y, Z, n, d, e and f are as described above, M is a hydrogen atom, lithium Represents an atom, sodium atom or potassium atom)
Is a group represented by
The manufacturing method of the diphosphine core type amphiphilic dendrimer represented by these.
<4> A bidentate phosphine ligand comprising the diphosphine core type amphiphilic dendrimer according to <1>.
<5> General formula (X) having a coordination structure containing the bidentate phosphine ligand according to <4>.

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G is a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the remaining represents 0, m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
L ¹ represents a halide ion, trifluoromethanesulfonate ion, nitrate ion or acetate ion]
Or general formula (XI)

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G is a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
L ² and L ³ are different from each other and represent a halide ion, trifluoromethanesulfonate ion, nitrate ion, acetate ion or allyl anion]
An amphiphilic dendrimer-fixed palladium (II) diphosphine complex represented by the formula:
<6> A catalyst for carbon-carbon bond generation reaction in water comprising at least one selected from the palladium-containing complex compounds according to <5>.

In the present invention, the substituent OG in the general formulas (I), (X) and (XI), the substituent OG ′ in the general formulas (III) and (V), the substituent OG ″ in the general formula (VI) and the general formula The substituent OG ^* in (VIII) is substituted at any of the 2,3,4,5,6 positions of the phenyl group.

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｘは水素原子、カルボキシル基、リチウムカルボキシレート基、ナトリウムカルボキシレート基又はカリウムカルボキシレート基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合はＸは水素原子以外の前述した官能基である）
で表される基である］ The novel diphosphine core type amphiphilic dendrimer of the present invention is represented by the following general formula (I).

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G is a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
Is a group represented by

About this dendrimer, the structure shown by each code | symbol in the substituent in the said formula is demonstrated concretely, and the structure is further clarified.
(1) U represents a divalent hydrocarbon group or a 1,1′-ferrocenylene group. The divalent hydrocarbon group includes a linear divalent aliphatic group and a divalent aromatic group. Examples of the linear divalent aliphatic group include alkylene groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, and a butylene group).
Examples of the divalent aromatic group include a 1,2-phenylene group, a 1,2-naphthylene group, a 2,3-naphthylene group, and a (1,1′-binaphthalene) 2,2′-diyl group.
(2) R ¹ , R ² , R ³ and R ⁴ represent a divalent hydrocarbon group, and this group includes a divalent aliphatic group and a divalent aromatic group. Divalent aliphatic groups include chain and cyclic groups. The divalent aromatic group includes an arylene group and an aralkylene group.
As the divalent aliphatic group, an alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, etc.), or 3 to 8 carbon atoms, preferably 5-6 cycloalkylene groups (for example, a cyclopentylene group, a cyclohexylene group, etc.) are mentioned.
Examples of the divalent aromatic group include arylene groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenylene group, naphthylene group, etc.), and aralkylene groups having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms. And groups represented by general formula (XII).
_{^{- (R 6) y -Ar- (}} R 7) z - (XII)
(In the formula, Ar represents an arylene group, R ⁶ and R ⁷ each represent a lower alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and y and z are 1 or 0, and one of these is 1)
(3) Y and Z are O, S, sulfinyl group (—SO—), sulfonyl group (—SO ₂ —), amide group [—NRCO—, —CONR— (where R is a hydrogen atom or an alkyl group)] or carbonyl A group (—CO—) is shown, preferably O, S or a sulfonyl group (—SO ₂ —).
(4) p, q, r, s and t each represent 0 or 1, but preferably p, q and r are 1 and s and t are 0, or p is 1 and q, r, s and t are 0.
(5) m is an integer of 0 or more, preferably 0-50. X represents a hydrogen atom, a carboxyl group (CO ₂ H), a lithium carboxylate group (CO ₂ Li), a sodium carboxylate group (CO ₂ Na) or a potassium carboxylate group (CO ₂ K). However, when m is 0, X is limited to the above functional group other than a hydrogen atom. When m is 1 or more, X is preferably a hydrogen atom.
(6) The generation number n of the repeating structure is an integer of 1 or more, preferably 1-6.
(7) Of d, e, and f, at least two indicate 1 and the rest indicate 0.
As an example of the group represented by the symbol G, the case where any two of d, e, and f are 1 and n = 3 is as follows.
_{^{- (R 1) p - (}} Y) q - (R 2) r - (Z) s - (R 3) t -C 6 H 3 - [O- (R 1) p - (Y) q - (R _{^{2) r - (Z) s}} - (R 3) t -C 6 H 3 - [O- (R 1) p - (Y) q - (R 2) r - (Z) s - (R 3) t _{-C 6 H 3 - [O- (} CH 2 CH 2 O) m -R 4 -X] 2] 2] 2

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ、Ｚ、ｄ、ｅ、ｆ、ｐ、ｑ、ｒ、ｓ及びｔは、前記と同じ意味を示す。）
この繰り返し構造として好ましくは、化１６中の各符号について、ｄ、ｆ及びｐが１、ｅ、ｑ、ｒ、ｓ及びｔが０、Ｒ^１がアルキレン基であるものが挙げられる。 In the dendrimer of the general formula (I), the repeating structure is represented by the general formula (XIII).

(In the formula, R ¹ , R ² , R ³ , Y, Z, d, e, f, p, q, r, s and t have the same meaning as described above.)
Preferred examples of this repeating structure include those in which d, f and p are 1, e, q, r, s and t are 0, and R ¹ is an alkylene group for each symbol in Chemical Formula 16.

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇ′は一般式（ＩＶ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｋは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表される基である］
で表されるジホスフィンオキシドコア型デンドリマーを、溶媒中で還元することにより製造することができる。
還元操作は、好ましくはトリエチルアミン等の三級アミン存在下トリクロロシラン、ヘキサクロロジシラン、クロロジフェニルシランやジクロロフェニルシランを還元剤に用い、また反応条件については、反応温度は、通常室温〜１５０℃の範囲で選ばれ、また反応時間は、反応温度や使用する溶媒等のその他の条件により異なり、一概に定めることはできないが、好ましくは６〜７２時間程度である。また溶媒としては、アセトニトリル、プロピオニトリルやトルエン、ベンゼン、キシレン等の炭化水素が好ましい。 The production of the diphosphine core type amphiphilic dendrimer (I) of the present invention will be described.
i) In the general formula (II), X is a hydrogen atom.

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G ′ is a compound represented by the general formula (IV)

Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, p, q , R, s, and t are each 0 or 1, n is an integer of 1 or more, k is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
Is a group represented by
The diphosphine oxide core type dendrimer represented by these can be manufactured by reduce | restoring in a solvent.
The reduction operation preferably uses trichlorosilane, hexachlorodisilane, chlorodiphenylsilane or dichlorophenylsilane as a reducing agent in the presence of a tertiary amine such as triethylamine, and the reaction conditions are usually in the range of room temperature to 150 ° C. The reaction time selected depends on other conditions such as the reaction temperature and the solvent used, and cannot be determined in general, but is preferably about 6 to 72 hours. Moreover, as a solvent, hydrocarbons, such as acetonitrile, propionitrile, toluene, benzene, xylene, are preferable.

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇ″は一般式（ＶＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｒ^５は炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｍは０以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表される基である］
で表されるジホスフィンコア型デンドリマーを、溶媒中で水酸化リチウム、水酸化ナトリウム又は水酸化カリウム等の塩基を用いて加水分解した後、酸、例えば塩酸または硫酸で処理しカルボキシル基体を得、場合によりさらに塩基、例えば水酸化リチウム、水酸化ナトリウム又は水酸化カリウムと中和反応させることにより製造することができる。
本ジホスフィンコア型デンドリマーを二座ホスフィン配位子として、含パラジウム錯体化合物（触媒）を調製する場合、この調製の直前に中和反応を行うのが好ましい。
加水分解操作の溶媒としては、これらの塩基化合物を溶解させる、メタノールやエタノール等のアルコールやジオキサン、テトラヒドロフラン、及びこれらの混合溶媒や、これらと水との混合溶媒が好ましい。酸処理も同様である。塩基との中和反応はこれらの溶媒のみならず、水のみでもよい。
加水分解操作は、通常室温〜１００℃の温度で行われる。酸処理や中和反応は、通常室温で行われる。
加水分解操作の反応温度は使用する溶媒等のその他の条件により異なり、一概に定めることはできないが、好ましくは２〜１２時間程度である。酸処理や中和反応は、多くの場合反応速度は速く、１分以内程度である。
この場合、原料となる一般式（ＶＩ）で表されるジホスフィンコア型デンドリマーは、対応するジホスフィンオキシドコア型デンドリマーを、前記ｉ）の場合と同様に還元することにより製造される。 ii) When X is a carboxyl group, a lithium carboxylate group, a sodium carboxylate group or a potassium carboxylate group in the general formula (II), the general formula (VI)

Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and G ″ is a general formula (VII).

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, R ⁵ is a hydrocarbon group, Y and Z are 2 consisting of O, S, SO, SO ₂ , an amide group or a carbonyl group. Valent linking group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, m is an integer of 0 or more, at least two of d, e and f are 1, and the rest are 0 )
Is a group represented by
In the case where the diphosphine core type dendrimer represented by the formula is hydrolyzed with a base such as lithium hydroxide, sodium hydroxide or potassium hydroxide in a solvent, then treated with an acid such as hydrochloric acid or sulfuric acid to obtain a carboxyl substrate. By further neutralizing with a base such as lithium hydroxide, sodium hydroxide or potassium hydroxide.
When preparing a palladium-containing complex compound (catalyst) using the present diphosphine core type dendrimer as a bidentate phosphine ligand, it is preferable to carry out a neutralization reaction immediately before this preparation.
As the solvent for the hydrolysis operation, alcohols such as methanol and ethanol, dioxane, tetrahydrofuran, a mixed solvent thereof, and a mixed solvent of these with water, which dissolve these basic compounds, are preferable. The same applies to the acid treatment. The neutralization reaction with the base may be performed not only with these solvents but also with water alone.
The hydrolysis operation is usually performed at a temperature of room temperature to 100 ° C. The acid treatment or neutralization reaction is usually performed at room temperature.
The reaction temperature of the hydrolysis operation varies depending on other conditions such as the solvent used, and cannot be generally determined, but is preferably about 2 to 12 hours. In many cases, the acid treatment and the neutralization reaction have a high reaction rate and are within 1 minute.
In this case, the diphosphine core type dendrimer represented by the general formula (VI) as a raw material is produced by reducing the corresponding diphosphine oxide core type dendrimer in the same manner as in the case of i).

［式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、Ｇ^＋は一般式（ＸＶ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｗは水素原子又はエステル基ＣＯ_２Ｒ^５（Ｒ^５は炭化水素基）、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合Ｗはエステル基ＣＯ_２Ｒ^５である）
で表される基である］
で表される、ジホスフィンオキシドコア型両親媒性デンドリマーは、一般式（ＸＶＩ）

（式中、Ｕは２価炭化水素基または１，１′−フェロセニレン基、水酸基は、フェニル基の２，３，４，５，６位のいずれかに置換される）
で表される含水酸基ホスフィンオキシドと、一般式（ＸＶＩＩ）

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ_２、アミド基又はカルボニル基から成る２価連結基、Ｗは水素原子又はエステル基ＣＯ_２Ｒ^５（Ｒ^５は炭化水素基）、Ｔはハロゲン原子、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示し、ｍは０以上の整数であるが、ｍが０の場合はＷはエステル基ＣＯ_２Ｒ^５である）
で表される含ハロゲンデンドロンを、溶媒中で塩基存在下、加熱することにより製造することができる。
塩基としては、炭酸カリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸水素ナトリウム等が挙げられる。
加熱温度は、通常室温から１５０℃の範囲で選ばれるが、５０℃から１００℃が好ましい。また、反応中、反応液は攪拌するのがよい。 The following general formula (XIV) corresponding to the raw material of i) and the raw material of the raw material of ii)

[Wherein U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, G ⁺ is a general formula (XV)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and W is hydrogen. Atom or ester group CO ₂ R ⁵ (R ⁵ is a hydrocarbon group), p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least two of d, e and f are 1 The remainder represents 0 and m is an integer greater than or equal to 0, but when m is 0, W is the ester group CO ₂ R ⁵ )
Is a group represented by
The diphosphine oxide core type amphiphilic dendrimer represented by the general formula (XVI)

(In the formula, U is a divalent hydrocarbon group or 1,1′-ferrocenylene group, and the hydroxyl group is substituted at any of the 2,3,4,5,6 positions of the phenyl group)
A hydroxyl group-containing phosphine oxide represented by the general formula (XVII)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and W is hydrogen. Atom or ester group CO ₂ R ⁵ (R ⁵ is a hydrocarbon group), T is a halogen atom, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, d, e and f At least two of them are 1 and the rest are 0, m is an integer of 0 or more, but when m is 0, W is an ester group CO ₂ R ⁵ )
Can be produced by heating in a solvent in the presence of a base.
Examples of the base include potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like.
The heating temperature is usually selected in the range of room temperature to 150 ° C, preferably 50 ° C to 100 ° C. Further, the reaction solution is preferably stirred during the reaction.

After completion of the reaction in the methods i) and ii), a reaction product is obtained by separating and removing the solvent and unreacted substances, and the production of the target product is confirmed by ¹ H-NMR and ³¹ P-NMR measurements. . However, in ii), the neutralization reaction using potassium hydroxide or the like after the production of the carboxyl substrate is a simple neutralization reaction, so that the formation of the desired carboxylate form is not confirmed, and the palladium-containing complex compound (catalyst) is added. Prepared.

（式中、Ｕ、Ｇは前述したものと同じ。Ｌ^１はハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、硝酸イオン又は酢酸イオンを示す。）
や一般式（ＸＩ）

（式中Ｕ、Ｇは前述したものと同じ。Ｌ^２とＬ^３はハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、硝酸イオン、酢酸イオン又はアリルアニオンを示す）
で表される、デンドリマーコア部のジホスフィン骨格を二座配位子とする両親媒性デンドリマー固定型パラジウム（ＩＩ）ジホスフィン錯体を製造することができる。 The diphosphine core type amphiphilic dendrimer represented by the general formula (I) of the present invention can be used as a bidentate ligand. One example of the reaction with the metal compound using the diphosphine core type amphiphilic dendrimer as a bidentate ligand will be described below.
Diphosphine core type amphiphilic dendrimer as the ligand and a general formula (XVIII) or (XIX) in a deoxygenated atmosphere
Pd (L ¹ ) ₂ (XVIII)
PdL ² L ³ (XIX)
(In the formula, L ¹ , L ² , and L ³ represent a halide ion, a trifluoromethanesulfonic acid ion, a nitrate ion, an acetate ion, and an allyl anion C ₃ H ₅ ^— , and L ² and L ³ are different from each other. (Allyl anions apply to L ² or L ³ )
And a palladium (II) compound represented by the composition:

(In the formula, U and G are the same as described above. L ¹ represents a halide ion, trifluoromethanesulfonate ion, nitrate ion or acetate ion.)
And general formula (XI)

(In the formula, U and G are the same as described above. L ² and L ³ represent a halide ion, trifluoromethanesulfonate ion, nitrate ion, acetate ion or allyl anion)
An amphiphilic dendrimer-fixed palladium (II) diphosphine complex having a diphosphine skeleton in the dendrimer core portion represented by the formula (2) can be produced.

This reaction is performed by dissolving a predetermined diphosphine core type amphiphilic dendrimer in a solvent and adding a palladium (II) compound. As the solvent, water or an organic solvent, preferably a halogenated hydrocarbon solvent such as dichloromethane is used.
The reaction can be allowed to proceed at about room temperature without special heating, but may be accelerated by heating. Further, the reaction solution is preferably stirred during the reaction.
After completion of the reaction, the reaction product is obtained by distilling off the solvent under reduced pressure, and the production of the target product is confirmed from the measurement of ¹ H-NMR and ³¹ P-NMR.

  Thus, the palladium (II) compound is immobilized by coordination with the dendrimer as a bidentate ligand. This novel amphiphilic dendrimer-fixed palladium (II) diphosphine complex is an organic reaction activated by various palladium (II) phosphine complex catalysts, for example, a carbon-carbon bond such as Suzuki-Miyaura reaction, Tsuji-Trost reaction, etc. Since the reaction can be promoted even in water by applying it to the production reaction, it is useful as a palladium (II) diphosphine complex catalyst for organic synthesis in water.

（式中、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１及びＲ^１２は、水素原子又は炭化水素基であって、Ｒ^８及びＲ^９、Ｒ^９及びＲ^１０、Ｒ^１１及びＲ^１２それぞれにおいて、いずれも炭化水素基の場合、両者は互いに結合して環を形成してもよい。またこれらの炭化水素基には触媒反応において関与しないアルコキシ基やアセチル基等の置換基を有していてもよい）
で表されるホウ酸誘導体と、一般式

（式中、Ｊはハロゲン原子、ヒドロキシル基、アセトキシ基（ＯＣＯＣＨ_３）、炭酸エステル基（ＯＣＯ_２Ｒ Ｒ：炭化水素基）、トリフルオロメタンスルホニル基（ＯＳＯ_２ＣＦ_３）又はメタンスルホニル基（ＯＳＯ_２ＣＨ_３）、Ｒ^１３、Ｒ^１４及びＲ^１５は、水素原子又は炭化水素基であって、Ｒ^１３及びＲ^１４、Ｒ^１３及びＲ^１５それぞれにおいて、いずれも炭化水素基の場合、両者は互いに結合して環を形成してもよい。またＲ^１３、Ｒ^１４及びＲ^１５それぞれが炭化水素基の場合、これらの炭化水素基には触媒反応において関与しないアルコキシ基やアセチル基等の置換基を有していてもよい。ｉは０又は１を示すが、０の場合、Ｊはヒドロキシル基、アセトキシ基及び炭酸エステル基以外の置換基である）
で表される有機化合物を、水中で反応させ、一般式

（式中、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１３、Ｒ^１４及びＲ^１５は前記と同じ意味を示し、ｉは０又は１を示す）
で表されるカップリング化合物を製造することができる。 The reaction 1 using the amphiphilic dendrimer-fixed palladium (II) diphosphine complex represented by the general formulas (X) and (XI) of the present invention as such a palladium (II) phosphine complex catalyst for organic synthesis in water An example is described below.
In the presence of a palladium (II) diphosphine complex as the catalyst,

(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each a hydrogen atom or a hydrocarbon group, and each of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , In the case where both are hydrocarbon groups, they may be bonded to each other to form a ring, and these hydrocarbon groups may have a substituent such as an alkoxy group or an acetyl group not involved in the catalytic reaction. Good)
A boric acid derivative represented by the general formula

(Wherein J represents a halogen atom, a hydroxyl group, an acetoxy group (OCOCH ₃ ), a carbonate group (OCO ₂ R R: hydrocarbon group), a trifluoromethanesulfonyl group (OSO ₂ CF ₃ ) or a methanesulfonyl group (OSO _2). CH ₃ ), R ¹³ , R ¹⁴ and R ¹⁵ are each a hydrogen atom or a hydrocarbon group, and each of R ¹³ and R ¹⁴ , R ¹³ and R ¹⁵ is a hydrocarbon group, they are bonded to each other. In addition, when each of R ¹³ , R ¹⁴ and R ¹⁵ is a hydrocarbon group, these hydrocarbon groups have a substituent such as an alkoxy group or an acetyl group that is not involved in the catalytic reaction. I represents 0 or 1, in which case J is a substituent other than a hydroxyl group, an acetoxy group and a carbonate group)
Is reacted in water to form a general formula

(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ and R ¹⁵ have the same meaning as described above, and i represents 0 or 1)
The coupling compound represented by these can be manufactured.

This reaction is carried out by dissolving or suspending the catalyst in water as a solvent and adding the raw material. You may use organic solvents, such as a dichloromethane, acetonitrile, toluene, as a solvent.
The reaction can be allowed to proceed at about room temperature, but it is preferable to promote the reaction by heating. During the reaction, the reaction solution is preferably stirred.
After completion of the reaction, the reaction solution is extracted, and the target substance can be obtained by separation and purification, for example, silica gel column chromatography.

  The amphiphilic dendrimer-fixed palladium (II) diphosphine complex catalyst of the present invention can be separated by filtration with a nanofilter (NF membrane) by increasing the number of generations of dendrimers. Therefore, by applying this catalyst to a liquid phase membrane reactor (membrane reactor), it is possible to perform continuous reaction by recycling the dendrimer-fixed catalyst. The complex catalyst can be recycled, and an energy-saving chemical process based on membrane separation is achieved. Therefore, this palladium (II) diphosphine complex catalyst contributes not only to the underwater process but also to the energy saving of the catalytic reaction process.

  As described above, the amphiphilic dendrimer-fixed palladium (II) diphosphine complex represented by the general formulas (X) and (XI) is useful as a palladium (II) phosphine complex catalyst. The carbon-carbon bond generation reaction activated by the palladium (II) phosphine complex catalyst can be efficiently promoted even in water.

  According to the present invention, a novel diphosphine core type amphiphilic dendrimer can be obtained, and this compound is useful as an amphiphilic bidentate phosphine ligand. Moreover, according to this invention, the novel amphiphilic dendrimer fixed type palladium (II) diphosphine complex which uses this as a ligand is obtained. This complex is effective as a palladium (II) complex catalyst for organic synthesis in water, and various carbon-carbon bond formation reactions such as the Suzuki-Miyaura reaction proceed efficiently in water. It contributes to efficient recycling.

Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.
In the examples, the deoxygenated solvent in the deoxygenated anhydrous xylene solution, deoxygenated anhydrous benzene solution, deoxygenated aqueous solution and the like was prepared by degassing with argon.

で表されるジホスフィンオキシドコア型デンドリマー１９９ｍｇの脱酸素無水キシレン溶液（９．３ｍｌ）に０℃にてトリエチルアミン１４８ｍｇと、トリクロロシラン１７２ｍｇの脱酸素キシレン溶液（０．９ｍｌ）を順次加え、室温で５分攪拌後１２０℃で２１時間攪拌し反応させた。
このようにして得られた反応溶液を、０℃にて炭酸水素ナトリウム４３５ｍｇの脱酸素水（２ｍｌ）とジクロロメタン（３０ｍｌ）の混合溶液に加え攪拌した後、無水硫酸マグネシウムで乾燥させ、次いでセライトろ過し、ろ液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（クロロホルム：メタノール＝２０：１）で精製した（無色油状、収量１７０ｍｇ、収率８６．７％）。
この生成物の核磁気共鳴スペクトル分析結果は次の通りである。
^１Ｈ−ＮＭＲ（５００ＭＨｚ，Ｃ_６Ｄ_６）δ／ｐｐｍ ７．３６（ｄｔ，８Ｈ，Ｊ＝８．５，３．０Ｈｚ），６．８３（ｄ，８Ｈ，Ｊ＝８．５Ｈｚ），６．６４（ｂｓ，８Ｈ），６．５４（ｓ，４Ｈ），４．６８（ｓ，８Ｈ），３．７８（ｔ，１６Ｈ，Ｊ＝４．９Ｈｚ），３．５２（ｔ，１６Ｈ，Ｊ＝４．９Ｈｚ），３．４８−３．４０（ｍ，４８Ｈ），３．３３（ｔ，１６Ｈ，Ｊ＝４．９Ｈｚ），３．１１（ｓ，２４Ｈ），２．２７（ｔ，４Ｈ，Ｊ＝３．８Ｈｚ）
^３１Ｐ−ＮＭＲ（２０２ＭＨｚ，Ｃ_６Ｄ_６）δ／ｐｐｍ −１６．０
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

Under the argon atmosphere, the following structural formula

148 mg of triethylamine and 172 mg of trichlorosilane (0.9 ml) were sequentially added to a 199 mg deoxygenated anhydrous xylene solution (9.3 ml) represented by the formula: The mixture was stirred for 21 hours at 120 ° C. and allowed to react.
The reaction solution thus obtained was added to a mixed solution of dehydrogenated water (2 ml) of sodium hydrogen carbonate (435 mg) and dichloromethane (30 ml) at 0 ° C., stirred, dried over anhydrous magnesium sulfate, and then filtered through Celite. The filtrate was evaporated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (chloroform: methanol = 20: 1) (colorless oil, yield 170 mg, yield 86.7%). .
The results of nuclear magnetic resonance spectrum analysis of this product are as follows.
¹ H-NMR (500 MHz, C ₆ D ₆ ) δ / ppm 7.36 (dt, 8H, J = 8.5, 3.0 Hz), 6.83 (d, 8H, J = 8.5 Hz), 6 .64 (bs, 8H), 6.54 (s, 4H), 4.68 (s, 8H), 3.78 (t, 16H, J = 4.9 Hz), 3.52 (t, 16H, J = 4.9 Hz), 3.48-3.40 (m, 48 H), 3.33 (t, 16 H, J = 4.9 Hz), 3.11 (s, 24 H), 2.27 (t, 4 H) , J = 3.8 Hz)
³¹ P-NMR (202 MHz, C ₆ D ₆ ) δ / ppm -16.0
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるジホスフィンコア型デンドリマー１．０６ｇのテトラヒドロフラン溶液（安定剤含有；３０ｍｌ）に、水酸化カリウム７２２ｍｇの無水メタノール溶液（１０ｍｌ）を加え、５０℃にて２４時間撹拌した。生成したカルボン酸塩を溶解させるため、反応開始後白色沈殿が生成するたびに１ｍｌずつ脱酸素水を加えた（計３ｍｌ）。
反応後、反応液を減圧下で溶媒留去し、得られた油状物質を１ｍｏｌ／ｌ塩酸（２４ｍｌ）に滴下して目的生成物を沈降させ、これを濾別し５５℃で１２時間真空乾燥した（白色粉体、９３４ｍｇ、収率９３．０％）。
この生成物の核磁気共鳴スペクトル分析結果は次の通りである。
^１Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＦ−ｄ_７）δ／ｐｐｍ １３．３４（ｂｓ，８Ｈ），８．０８（ｄ，１６Ｈ，Ｊ＝８．２Ｈｚ），７．６５（ｄ，１６Ｈ，Ｊ＝８．２Ｈｚ），７．３８（ｄｔ，８Ｈ，Ｊ＝８．４，３．４Ｈｚ），７．０８（ｄ，８Ｈ，Ｊ＝８．４Ｈｚ），６．８７（ｄ，８Ｈ，Ｊ＝２．１Ｈｚ），６．７８（ｔ，４Ｈ，Ｊ＝２．１Ｈｚ），５．２７（ｓ，１６Ｈ），５．１２（ｓ，８Ｈ），２．０８（ｂｓ，４Ｈ）
^３１Ｐ−ＮＭＲ（２０２ＭＨｚ，ＤＭＦ−ｄ_７）δ／ｐｐｍ −１６．７４
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

Under the argon atmosphere, the following structural formula

To a tetrahydrofuran solution (containing a stabilizer; 30 ml) of 1.06 g of the diphosphine core type dendrimer represented by the formula, an anhydrous methanol solution (10 ml) of potassium hydroxide 722 mg was added and stirred at 50 ° C. for 24 hours. In order to dissolve the produced carboxylate, 1 ml of deoxygenated water was added each time a white precipitate was formed after the start of the reaction (3 ml in total).
After the reaction, the solvent of the reaction solution was distilled off under reduced pressure, and the obtained oily substance was added dropwise to 1 mol / l hydrochloric acid (24 ml) to precipitate the target product, which was filtered off and vacuum-dried at 55 ° C. for 12 hours. (White powder, 934 mg, yield 93.0%).
The results of nuclear magnetic resonance spectrum analysis of this product are as follows.
¹ H-NMR (500 MHz, DMF-d ₇ ) δ / ppm 13.34 (bs, 8H), 8.08 (d, 16H, J = 8.2 Hz), 7.65 (d, 16H, J = 8 .2 Hz), 7.38 (dt, 8H, J = 8.4, 3.4 Hz), 7.08 (d, 8H, J = 8.4 Hz), 6.87 (d, 8H, J = 2. 1 Hz), 6.78 (t, 4H, J = 2.1 Hz), 5.27 (s, 16H), 5.12 (s, 8H), 2.08 (bs, 4H)
³¹ P-NMR (202 MHz, DMF-d ₇ ) δ / ppm -16.74
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるジホスフィンコア型デンドリマー１．８４ｇのテトラヒドロフラン溶液（安定剤含有；３０ｍｌ）に、水酸化カリウム１．２７ｇの無水メタノール溶液（１０ｍｌ）を加え、５０℃にて２４時間撹拌した。生成したカルボン酸塩を溶解させるため、反応開始後白色沈殿が生成するたびに１ｍｌずつ脱酸素水を加えた（計３ｍｌ）。
反応後、反応液を減圧下で溶媒留去し、得られた油状物質を１ｍｏｌ／ｌ塩酸（４８ｍｌ）に滴下して目的生成物を沈降させ、これを濾別し５５℃で１２時間真空乾燥した（白色粉体、１．６２ｇ、収率７２．３％）。
この生成物の核磁気共鳴スペクトル分析結果は次の通りである。
^１Ｈ−ＮＭＲ（５００ＭＨｚ，ＤＭＦ−ｄ_７）δ／ｐｐｍ １３．３４（ｂｓ，１６Ｈ），８．０６（ｄ，３２Ｈ，Ｊ＝８．２Ｈｚ），７．６３（ｄ，３２Ｈ，Ｊ＝８．２Ｈｚ），７．３４（ｄｔ，８Ｈ，Ｊ＝８．５，３．４Ｈｚ），７．０６（ｄ，８Ｈ，Ｊ＝８．５Ｈｚ），６．８５（ｄ，１６Ｈ、Ｊ＝１．８Ｈｚ），６．８２（ｄ，８Ｈ，Ｊ＝１．５Ｈｚ），６．７６（ｂｓ，８Ｈ），６．７２（ｂｓ，４Ｈ），５．２５（ｓ，３２Ｈ），５．１１（ｓ，２４Ｈ），２．０５（ｂｓ，４Ｈ）
^３１Ｐ−ＮＭＲ（２０２ＭＨｚ，ＤＭＦ−ｄ_７）δ／ｐｐｍ −１９．０
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

Under the argon atmosphere, the following structural formula

An anhydrous methanol solution (10 ml) of 1.27 g of potassium hydroxide was added to a tetrahydrofuran solution (containing a stabilizer; 30 ml) of 1.84 g of the diphosphine core type dendrimer represented by the formula, and the mixture was stirred at 50 ° C. for 24 hours. In order to dissolve the produced carboxylate, 1 ml of deoxygenated water was added each time a white precipitate was formed after the start of the reaction (3 ml in total).
After the reaction, the solvent of the reaction solution was distilled off under reduced pressure, and the obtained oily substance was added dropwise to 1 mol / l hydrochloric acid (48 ml) to precipitate the desired product, which was filtered off and vacuum-dried at 55 ° C. for 12 hours. (White powder, 1.62 g, yield 72.3%).
The results of nuclear magnetic resonance spectrum analysis of this product are as follows.
¹ H-NMR (500 MHz, DMF-d ₇ ) δ / ppm 13.34 (bs, 16 H), 8.06 (d, 32 H, J = 8.2 Hz), 7.63 (d, 32 H, J = 8 .2 Hz), 7.34 (dt, 8H, J = 8.5, 3.4 Hz), 7.06 (d, 8H, J = 8.5 Hz), 6.85 (d, 16H, J = 1. 8 Hz), 6.82 (d, 8H, J = 1.5 Hz), 6.76 (bs, 8H), 6.72 (bs, 4H), 5.25 (s, 32H), 5.11 (s) , 24H), 2.05 (bs, 4H)
³¹ P-NMR (202 MHz, DMF-d ₇ ) δ / ppm -19.0
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表される含パラジウム化合物であることが確認された。 Under an argon atmosphere, bis (π-allyl) dichlorodipalladium (II) [PdClC ₃ H ₅ was added to 36.0 mg of N, N-dimethylformamide solution (0.75 ml) of the diphosphine core-type dendrimer obtained in Example 3. ₂ 1.6 mg was added and the reaction was allowed to stir at room temperature for 5 minutes.
The solvent thus obtained was distilled off under reduced pressure, followed by vacuum drying at 50 ° C. for 4 days to obtain 40.9 mg of the desired product.
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, DMF-d ₇ ) δ / ppm 13.35 (s, 16 H), 8.08 (d, 32 H, J = 8.2 Hz), 7.73 (t, 8 H, J = 8) .2 Hz), 7.64 (d, 32 H, J = 8.2 Hz), 7.21 (d, 8 H, J = 8.2 Hz), 6.90-6.75 (m, 36 H), 6.04 (Quin, 1H, J = 10.5 Hz), 5.27 (s, 32H), 5.18 (s, 8H), 5.14 (s, 16H), 4.37 (bs, 2H) 3.62 (D, 1H, J = 6.7 Hz), 2.79 (bs, 4H), 2.64 (d, 1H, J = 11.9 Hz))
³¹ P-NMR (202 MHz, DMF-d ₇ ) δ / ppm 50.1
From these analysis results, this product is represented by the formula (XX)

It was confirmed that this was a palladium-containing compound represented by

で表される含パラジウム化合物からなるパラジウム（II）ホスフィン錯体触媒含有溶液を調製した。この溶液にヨードベンゼン６８１ｍｇ、４−アセチルフェニルホウ酸８２１ｍｇ、炭酸カリウム２．０７ｇ、及び脱酸素水６．７ｍｌを順次加え、６０℃にて３６時間攪拌し反応させた。
反応終了後、反応液をジエチルエーテルで４回抽出し、有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。濾過後濾液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４０：１）で分離精製して以下の構造式

で表されるカップリング生成物３８９ｍｇ（収率５９％）を得た。 A potassium carboxylate form was prepared from 74.8 mg of the diphosphine core type dendrimer obtained in Example 2 and 19.8 mg of potassium hydroxide in deoxygenated water (2.5 ml) under an argon atmosphere, and bis (π-allyl) was prepared. ) Dichlorodipalladium (II) [PdClC ₃ H ₅ ] _{2 (} 7.2 mg) was added, and the mixture was stirred at room temperature for 15 minutes to give the formula (XXI)

The palladium (II) phosphine complex catalyst containing solution which consists of a palladium containing compound represented by these was prepared. To this solution, 681 mg of iodobenzene, 821 mg of 4-acetylphenylboric acid, 2.07 g of potassium carbonate, and 6.7 ml of deoxygenated water were sequentially added, and the mixture was reacted by stirring at 60 ° C. for 36 hours.
After completion of the reaction, the reaction solution was extracted four times with diethyl ether, and the organic layer was washed with saturated brine and dried over magnesium sulfate. After filtration, the filtrate was evaporated under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography (hexane: ethyl acetate = 40: 1) to obtain the following structural formula.

389 mg (yield 59%) of a coupling product represented by the formula:

Claims (6)

Formula (I)

[In the formula, U represents an alkylene group having 1 to 4 carbon atoms , or 1,1′-ferrocenylene group, and G represents a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
Is a group represented by
A diphosphine core type amphiphilic dendrimer represented by the formula: Formula (III)

[Wherein U is an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G ′ is a group represented by the general formula (IV)

Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, p, q , R, s, and t are each 0 or 1, n is an integer of 1 or more, k is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
Is a group represented by
A diphosphine oxide core-type dendrimer represented by the general formula (V):

(In the formula, U is an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G ′ is as described above.)
The manufacturing method of the diphosphine core type amphiphilic dendrimer represented by these. Formula (VI)

[Wherein U is an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G ″ is a general formula (VII)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, R ⁵ is a hydrocarbon group, Y and Z are 2 consisting of O, S, SO, SO ₂ , an amide group or a carbonyl group. Valent linking group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, m is an integer of 0 or more, at least two of d, e and f are 1, and the rest are 0 )
Is a group represented by
A diphosphine core-type dendrimer represented by the general formula is hydrolyzed with a base in a solvent and then reacted with an acid, optionally further reacted with lithium hydroxide, sodium hydroxide or potassium hydroxide (VIII)

[In the formula, U represents an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G ^* represents a general formula (IX)

Wherein R ¹ , R ² , R ³ , R ⁴ , p, q, r, s, t, Y, Z, n, d, e and f are as described above, M is a hydrogen atom, lithium Represents an atom, sodium atom or potassium atom)
Is a group represented by
The manufacturing method of the diphosphine core type amphiphilic dendrimer represented by these. A bidentate phosphine ligand comprising the diphosphine core type amphiphilic dendrimer according to claim 1. A general formula (X) having a coordination structure comprising the bidentate phosphine ligand according to claim 4

[In the formula, U represents an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G represents a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
L ¹ represents a halide ion, trifluoromethanesulfonate ion, nitrate ion or acetate ion]
Or general formula (XI)

[In the formula, U represents an alkylene group having 1 to 4 carbon atoms or 1,1′-ferrocenylene group, and G represents a general formula (II)

(Wherein R ¹ , R ² , R ³ and R ⁴ are divalent hydrocarbon groups, Y and Z are divalent linking groups comprising O, S, SO, SO ₂ , an amide group or a carbonyl group, and X is hydrogen. Atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, and at least of d, e and f 2 represents 1 and the rest represents 0, and m is an integer of 0 or more, but when m is 0, X is the above-described functional group other than a hydrogen atom)
And L ² and L ³ are different from each other and represent a halide ion, a trifluoromethanesulfonate ion, a nitrate ion, an acetate ion, or an allyl anion.
An amphiphilic dendrimer-fixed palladium (II) diphosphine complex represented by the formula: A catalyst for carbon-carbon bond generation reaction in water comprising at least one selected from the palladium-containing complex compounds according to claim 5.