JP4822410B2 - Phosphine-encapsulated amphiphilic dendrimer, process for producing the same, phosphine ligand and palladium-containing complex catalyst having a coordination structure thereof - Google Patents

Description

  The present invention relates to a novel phosphine-encapsulated amphiphilic dendrimer, a method for producing the same, a phosphine ligand comprising the dendrimer, and a palladium-containing complex catalyst 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 the phosphine skeleton as a ligand (see Non-Patent Document 5).

  In addition, since the size of the dendrimer-fixed organometallic catalyst is nano-level, it can be continuously reacted by recycling the catalyst by application to a liquid phase membrane reactor (membrane reactor) (Non-Patent Document 6, 7).

“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 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 problem of the present invention is that it is useful as a phosphine ligand as a raw material for an organometallic complex catalyst for organic synthesis in water. The object is to provide a phosphine-encapsulated amphiphilic dendrimer having a phosphine skeleton in the part.

  As a result of intensive studies on the phosphine-encapsulated amphiphilic dendrimer having a hydrophilic group at the end portion of the dendrimer described above, the present inventors have reduced the corresponding phosphine oxide or the phosphine-encapsulated dendrimer terminal in a solvent. A novel phosphine-encapsulated amphiphilic dendrimer can be easily obtained by hydrolysis of the ester group of the phosphine, and this phosphine-encapsulated amphiphilic dendrimer can be used as a ligand. The amphiphilic dendrimer-fixed palladium phosphine complex, which effectively promotes the organic reaction activated by the palladium phosphine complex catalyst in water, is found to be useful as a novel complex catalyst for organic synthesis in water, The present invention has been completed based on these findings.

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０のアルキレン基、Ｒ^４はＣＨ_２またはＣＨ_２Ｃ_６Ｈ_４、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は１、ｑ、ｒ、ｓ及びｔはそれぞれ０、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ホスフィン内包型両親媒性デンドリマー。
（２） 一般式（ＩＩＩ）

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇ′は一般式（ＩＶ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０のアルキレン基、Ｒ^４はＣＨ_２またはＣＨ_２Ｃ_６Ｈ_４、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は１、ｑ、ｒ、ｓ及びｔはそれぞれ０、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］
で表されるホスフィンオキシド内包型デンドリマーを、溶媒中で還元することを特徴とする一般式（Ｖ）

（式中、ｕ、ｖ、Ｇ′は上記のとおりである）
で表されるホスフィン内包型両親媒性デンドリマーの製造方法。
（３） 一般式（ＶＩ）

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇ″は一般式（ＶＩＩ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０のアルキレン基、Ｒ^４はＣＨ_２またはＣＨ_２Ｃ_６Ｈ_４、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は１、ｑ、ｒ、ｓ及びｔはそれぞれ０、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］
で表されるホスフィン内包型デンドリマーを、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を用いて加水分解し、場合によりさらに酸と反応させることを特徴とする一般式（ＶＩＩＩ）

［式中、ｕ、ｖ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］
で表されるホスフィン内包型両親媒性デンドリマーの製造方法。
（４） 前記（１）記載のホスフィン内包型両親媒性デンドリマーからなるホスフィン配位子。
（５） 前記（４）記載の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０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０のアルキレン基、Ｒ^４はＣＨ_２またはＣＨ_２Ｃ_６Ｈ_４、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は１、ｑ、ｒ、ｓ及びｔはそれぞれ０、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^１はハロゲン化物イオン、硝酸イオン又は酢酸イオン、ｇは１又は２を示す］
及び一般式（ＸＩ）

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は炭素数１〜１０のアルキレン基、Ｒ^４はＣＨ_２またはＣＨ_２Ｃ_６Ｈ_４、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は１、ｑ、ｒ、ｓ及びｔはそれぞれ０、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、硝酸イオン、酢酸イオン又はアリルアニオンを示し、ｈは１又は２を示すが、Ｌ^２及びＬ^３の何れかがアリルアニオンの場合、ｈは１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）ホスフィン錯体の中から選ばれた少なくとも１種からなる含パラジウム錯体触媒。 That is, according to the present invention, the following inventions are provided.
(1) General formula (I)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

(Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0, n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
Is a group represented by
A phosphine-encapsulated amphiphilic dendrimer characterized by being represented by the formula:
(2) General formula (III)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ′ is represented by the general formula (IV)

(Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group comprising a carbonyl group, p is 1, q, r, s and t are each 0, n is an integer of 1 or more, k is an integer of 1 or more, and at least two of d, e and f are 1 And the rest indicate 0)
Is a group represented by
A phosphine oxide-encapsulated dendrimer represented by the general formula (V):

(Wherein u, v and G ′ are as described above)
The manufacturing method of the phosphine inclusion type amphiphilic dendrimer represented by these.
(3) General formula (VI)

[Wherein u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ″ is represented by the general formula (VII)

Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , R ⁵ is a hydrocarbon group, Y and Z are O, S, A divalent linking group comprising SO, SO ₂ , an amide group or a carbonyl group, p is 1, q, r, s and t are each 0, n is an integer of 1 or more, m is an integer of 0 or more, d, e and (At least two of f indicate 1 and the rest indicate 0)
Is a group represented by
The phosphine-encapsulated dendrimer represented by the general formula (VIII) is hydrolyzed with lithium hydroxide, sodium hydroxide or potassium hydroxide in a solvent and optionally further reacted with an acid.

[Wherein u and v are 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 phosphine inclusion type amphiphilic dendrimer represented by these.
(4) A phosphine ligand comprising the phosphine-encapsulated amphiphilic dendrimer according to (1).
(5) General formula (X) having a coordination structure containing the phosphine ligand according to (4)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

(Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0, n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
L ¹ is a halide ion, nitrate ion or acetate ion, and g is 1 or 2.]
And general formula (XI)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

(Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0, n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
L ² and L ³ are different from each other and represent a halide ion, a nitrate ion, an acetate ion or an allyl anion, and h represents 1 or 2, but either L ² or L ³ is allyl. In the case of an anion, h represents 1]
A palladium-containing complex catalyst comprising at least one selected from the amphiphilic dendrimer-fixed palladium (II) phosphine complexes represented by the formula:

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０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇは一般式（ＩＩ）

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ₂、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 phosphine-encapsulated amphiphilic dendrimer of the present invention is represented by the following general formula (I).

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the 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) 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.
Examples of the divalent aliphatic group include alkylene groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (for example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, isobutylene group, etc.), and 3 to 8 carbon atoms. , Preferably 5-6 cycloalkylene groups (for example, cyclopentylene group, 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)
(2) Y and Z are O, S, a sulfinyl group (—SO—), a sulfonyl group (—SO ₂ —), an 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 —).
(3) 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.
(4) 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.
(5) The generation number n of the repeating structure is an integer of 1 or more, preferably 1-6.
(6) At least two of d, e, and f are 1 and the rest are 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、Ｒ¹、Ｒ²、Ｒ³、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、Ｒ¹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).

(Wherein 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０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇ′は一般式（ＩＶ）

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ₂、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］
で表されるホスフィンオキシド内包型デンドリマーを、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やヘキサクロロジ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、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 phosphine-encapsulated amphiphilic dendrimer (I) of the present invention will be described.
i) In the general formula (II), X is a hydrogen atom.

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ′ is 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
Can be produced by reducing in a solvent.
The reduction operation preferably uses trichlorosilane or hexachlorodisilane as a reducing agent in the presence of a tertiary amine such as triethylamine, and the reaction conditions are usually selected in the range of room temperature to 150 ° C., and the reaction time is Depending on the reaction temperature and other conditions such as the solvent used, it cannot be determined in general, but it is preferably about 6 to 72 hours. Moreover, as a solvent, hydrocarbons, such as toluene, benzene, xylene, are preferable.

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇ″は一般式（ＶＩＩ）

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は２価炭化水素基、Ｒ⁵は炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ₂、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］
で表されるホスフィン内包型デンドリマーを、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を用いて加水分解し、場合によりさらに酸、例えば塩酸または硫酸を用い中和反応させることにより製造することができる。
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。
加水分解操作は、通常室温〜１００℃の温度で行われる。中和反応は、通常室温で行われる。
加水分解操作の反応時間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。中和反応は、多くの場合反応速度は速く、反応時間は３０分以内程度である。
この場合、原料となる一般式（ＶＩ）で表されるホスフィン内包型デンドリマーは、対応するホスフィンオキシド内包型デンドリマーを、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 an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ″ is represented by the 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 phosphine-encapsulated dendrimer represented by the formula is produced by hydrolyzing with lithium hydroxide, sodium hydroxide or potassium hydroxide in a solvent, and optionally further neutralizing with an acid such as hydrochloric acid or sulfuric acid. be able to.
The solvent is preferably an alcohol such as methanol or ethanol, dioxane, tetrahydrofuran, a mixed solvent thereof, or a mixed solvent of these with water, in which these basic compounds are dissolved.
The hydrolysis operation is usually performed at a temperature of room temperature to 100 ° C. The neutralization reaction is usually performed at room temperature.
The reaction time of the hydrolysis operation varies depending on other conditions such as the solvent used, and cannot be generally defined, but is preferably about 2 to 12 hours. In many cases, the neutralization reaction has a high reaction rate and a reaction time of about 30 minutes or less.
In this case, the phosphine-encapsulated dendrimer represented by the general formula (VI) as a raw material is produced by reducing the corresponding phosphine oxide-encapsulated dendrimer in the same manner as in the case of i).

［式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、Ｇ^☆は一般式（ＸＶ）

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ₂、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ＣＯ₂Ｒ⁵（Ｒ⁵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の場合はＷはエステル基ＣＯ₂Ｒ⁵である）
で表される基である］
で表される、ホスフィンオキシド内包型両親媒性デンドリマーは、一般式（ＸＶＩ）

（式中、ｕは０〜２の整数、ｖは１〜３の整数であって、かつｕ＋ｖ＝３であり、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、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は２価炭化水素基、Ｙ及びＺはＯ、Ｓ、ＳＯ、ＳＯ₂、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ＣＯ₂Ｒ⁵（Ｒ⁵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ＣＯ₂Ｒ⁵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。 In each of the production methods i) and ii), the raw material and the following general formula (XIV) corresponding to the raw material

[Wherein u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and 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 consisting of 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 phosphine oxide-encapsulated amphiphilic dendrimer represented by the general formula (XVI)

(In the formula, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and the hydroxyl group is in any of positions 2, 3, 4, 5, and 6 of the phenyl group. Replaced)
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 consisting of 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. .

（式中、ｕ、ｖ、Ｇは前述したものと同じ、Ｌ¹はハロゲン化物イオン、硝酸イオン又は酢酸イオン、ｇは１又は２を示す。）
や一般式（ＸＩ）

（式中、ｕ、ｖ、Ｇは前述したものと同じ、Ｌ²とＬ³はハロゲン化物イオン、硝酸イオン、酢酸イオン又はアリルアニオンを示し、ｈは１又は２を示すが、Ｌ²及びＬ³の何れかがアリルアニオンの場合、ｈは１である）
で表される、デンドリマーコア部のホスフィン骨格を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）ホスフィン錯体を製造することができる。 The phosphine-encapsulated amphiphilic dendrimer represented by the general formula (I) of the present invention can be used as a ligand. One example of the reaction with the metal compound having the phosphine-encapsulated amphiphilic dendrimer as a ligand will be described below.
In a deoxygenated atmosphere, the phosphine-encapsulated amphiphilic dendrimer as the ligand and the general formula (XVIII) or (XIX)
Pd (L ¹ ) ₂ (XVIII)
PdL ² L ³ (XIX)
(Wherein L ^1, L ^2, and L ³ is a halide ion, nitrate ion, acetate ion, allyl anions C ₃ H ₅ ^-. Indicates, also L ² and L ³ are different from each other, however allyl anion L ² Or applies to L ³ )
And a palladium (II) compound represented by the composition:

(Wherein u, v and G are the same as those described above, L ¹ represents a halide ion, nitrate ion or acetate ion, and g represents 1 or 2)
And general formula (XI)

(Wherein u, v and G are the same as those described above, L ² and L ³ represent a halide ion, nitrate ion, acetate ion or allyl anion, and h represents 1 or 2, but L ² and L ^If any of ³ is an allyl anion, h is 1)
An amphiphilic dendrimer-fixed palladium (II) phosphine complex having a phosphine skeleton of the dendrimer core portion as a ligand can be produced.

This reaction is carried out by dissolving a predetermined phosphine-encapsulated 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 ligand. This amphiphilic dendrimer-fixed palladium (II) phosphine complex is an organic reaction activated by various palladium (II) phosphine complex catalysts, for example, a carbon-carbon bond forming reaction such as Suzuki-Miyaura reaction, Tsuji-Trost reaction, etc. Since the reaction can be promoted even in water, it is useful as a palladium (II) phosphine complex catalyst for organic synthesis in water.

（式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹及びＲ¹²は、水素原子又は炭化水素基であって、Ｒ⁸及びＲ⁹、Ｒ⁹及びＲ¹⁰、Ｒ¹¹及びＲ¹²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）
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、アセトキシ基（ＯＣＯＣＨ₃）、炭酸エステル基（ＯＣＯ₂Ｒ Ｒ：炭化水素基）、トリフルオロメタンスルホニル基（ＯＳＯ₂ＣＦ₃）又はメタンスルホニル基（ＯＳＯ₂ＣＨ₃）、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、水素原子又は炭化水素基であって、Ｒ¹³及びＲ¹⁴、Ｒ¹³及びＲ¹⁵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。ｉは０又は１を示すが、０の場合、Ｊは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、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は前記と同じ意味を示し、ｉは０又は１を示す）
で表される炭化水素を製造することができる。 The reaction 1 using the amphiphilic dendrimer-fixed palladium (II) phosphine 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) phosphine complex as the catalyst,

(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are hydrogen atoms or hydrocarbon groups, 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)
A boric acid derivative represented by the general formula

(In the formula, J is a halogen atom, an acetoxy group (OCOCH ₃ ), a carbonate group (OCO ₂ RR: 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 when each of R ¹³ and R ¹⁴ , R ¹³ and R ¹⁵ is a hydrocarbon group, they are bonded to each other to form a ring. I represents 0 or 1, in which case J is a substituent other than 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)
Can be produced.

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) phosphine 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, application of this catalyst to a liquid phase membrane reactor (membrane reactor) enables continuous reaction by recycling of the catalyst, thereby achieving an energy-saving chemical process. Therefore, this palladium (II) phosphine 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) phosphine complex represented by the general formulas (X) and (XI) is useful as a palladium (II) phosphine complex catalyst. The organic reaction activated by the palladium (II) phosphine complex catalyst can be promoted efficiently even in water.

  According to the present invention, a novel phosphine-encapsulated amphiphilic dendrimer can be obtained, and this compound is useful as an amphiphilic phosphine ligand. The amphiphilic dendrimer-fixed palladium (II) phosphine complex having this as a ligand is effective as a palladium (II) complex catalyst for organic synthesis in water, and various carbon-carbons such as Suzuki-Miyaura reaction, for example. It contributes to the efficient progress of bond formation reactions in water.

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.

で表されるホスフィンオキシド内包型デンドリマー７１７．５ｍｇの脱酸素無水キシレン溶液（２．５ｍｌ）に、０℃にてトリエチルアミン２５５．５ｍｇの脱酸素無水キシレン溶液（３ｍｌ）とトリクロロシラン３３５ｍｇの脱酸素無水キシレン溶液（２ｍｌ）を順次加え、室温で３０分攪拌後、１２０℃で１２時間攪拌し、反応させた。
このようにして得られた反応液に、０℃にて水酸化ナトリウム４００ｍｇの水溶液（１ｍｌ）を滴下し１５分攪拌した後、無水硫酸マグネシウムで乾燥させ、次いでセライト濾過し、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（クロロホルム：メタノール＝１５：１）で精製した（無色油状、収量６２４．５ｍｇ、収率８７．９％）。
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，Ｃ₆Ｄ₆）δ／ｐｐｍ ７．４２（ｔ，６Ｈ，Ｊ＝８．２Ｈｚ），６．８９（ｄ，６Ｈ，Ｊ＝８．２Ｈｚ），６．６５（ｓ，６Ｈ），６．５４（ｓ，３Ｈ），４．７０（ｓ，６Ｈ），３．７９（ｔ，１２Ｈ，Ｊ＝４．７Ｈｚ），３．５４−３．４６（ｍ，４８Ｈ），３．３４（ｔ，１２Ｈ，Ｊ＝４．９Ｈｚ），３．１３（ｓ，１８Ｈ）
³¹Ｐ−ＮＭＲ（２０２ＭＨｚ，Ｃ₆Ｄ₆）δ／ｐｐｍ −９．７
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

A deoxygenated anhydrous xylene solution (2.5 ml) containing 717.5 mg of a phosphine oxide-encapsulated dendrimer represented by the following formula: A xylene solution (2 ml) was sequentially added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 120 ° C. for 12 hours to be reacted.
To the reaction solution thus obtained, an aqueous solution (1 ml) of 400 mg of sodium hydroxide was added dropwise at 0 ° C., stirred for 15 minutes, dried over anhydrous magnesium sulfate, filtered through celite, and the filtrate was reduced under reduced pressure. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography (chloroform: methanol = 15: 1) (colorless oil, yield 624.5 mg, yield 87.9%).
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 7.42 (t, 6H, J = 8.2 Hz), 6.89 (d, 6H, J = 8.2 Hz), 6.65 (s , 6H), 6.54 (s, 3H), 4.70 (s, 6H), 3.79 (t, 12H, J = 4.7 Hz), 3.54-3.46 (m, 48H), 3.34 (t, 12H, J = 4.9 Hz), 3.13 (s, 18H)
³¹ P-NMR (202 MHz, C ₆ D ₆ ) δ / ppm −9.7
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるホスフィンオキシド内包型デンドリマー４０４．０ｍｇの脱酸素無水キシレン溶液（２ｍｌ）に、０℃にてトリエチルアミン７５．４ｍｇの脱酸素無水キシレン溶液（１ｍｌ）とトリクロロシラン８７．２ｍｇの脱酸素無水キシレン溶液（１ｍｌ）を順次加え、室温で３０分攪拌後、１２０℃で１６時間攪拌し、反応させた。
このようにして得られた反応液に、０℃にて水酸化ナトリウム９７ｍｇの水溶液（０．５ｍｌ）を滴下し１５分攪拌した後、無水硫酸マグネシウムで乾燥させ、次いでセライト濾過し、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（ジクロロメタン：エタノール＝３０：１）で精製した（無色油状、収量３２１．３ｍｇ、収率７９．９％）。
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，Ｃ₆Ｄ₆）δ／ｐｐｍ ７．４４（ｔ，６Ｈ，Ｊ＝８．４Ｈｚ），６．９２（ｄ，６Ｈ，Ｊ＝８．４Ｈｚ），６．７７（ｄ，６Ｈ，Ｊ＝２．２Ｈｚ），６．７４（ｔ，３Ｈ，Ｊ＝２．２Ｈｚ），６．６９（ｄ，１２Ｈ，Ｊ＝２．４Ｈｚ），６．５６（ｔ，６Ｈ，Ｊ＝２．４Ｈｚ），４．７７（ｓ，１２Ｈ），４．７４（ｓ，６Ｈ），３．８３（ｔ，２４Ｈ，Ｊ＝４．９Ｈｚ），３．５６（ｔ，２４Ｈ，Ｊ＝４．９Ｈｚ），３．５０−３．４６（ｍ，７２Ｈ），３．３５（ｔ，２４Ｈ，Ｊ＝４．９Ｈｚ），３．１３（ｓ，３６Ｈ）
³¹Ｐ−ＮＭＲ（２０２ＭＨｚ，Ｃ₆Ｄ₆）δ／ｐｐｍ −９．６
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

A deoxygenated anhydrous xylene solution (2 ml) containing 404.0 mg of a phosphine oxide-containing dendrimer represented by the formula: A xylene solution (1 ml) was sequentially added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 120 ° C. for 16 hours to be reacted.
An aqueous solution (0.5 ml) of sodium hydroxide 97 mg was added dropwise to the reaction solution thus obtained at 0 ° C., stirred for 15 minutes, dried over anhydrous magnesium sulfate, then filtered through celite, and the filtrate was reduced in pressure. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (dichloromethane: ethanol = 30: 1) (colorless oil, yield 321.3 mg, yield 79.9%).
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 7.44 (t, 6H, J = 8.4 Hz), 6.92 (d, 6H, J = 8.4 Hz), 6.77 (d , 6H, J = 2.2 Hz), 6.74 (t, 3H, J = 2.2 Hz), 6.69 (d, 12H, J = 2.4 Hz), 6.56 (t, 6H, J = 2.4 Hz), 4.77 (s, 12 H), 4.74 (s, 6 H), 3.83 (t, 24 H, J = 4.9 Hz), 3.56 (t, 24 H, J = 4. 9 Hz), 3.50-3.46 (m, 72 H), 3.35 (t, 24 H, J = 4.9 Hz), 3.13 (s, 36 H)
³¹ P-NMR (202 MHz, C ₆ D ₆ ) δ / ppm −9.6
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるホスフィンオキシド内包型デンドリマー９６７．４ｍｇの脱酸素無水キシレン溶液（５ｍｌ）に、０℃にてトリエチルアミン１７２．６ｍｇの脱酸素無水キシレン溶液（２．５ｍｌ）とトリクロロシラン２１８．６ｍｇの脱酸素無水キシレン溶液（１ｍｌ）を順次加え、室温で２０分攪拌後、１１０℃で１４時間攪拌し、反応させた。
このようにして得られた反応液に、０℃にて水酸化ナトリウム２３０ｍｇの水溶液（１ｍｌ）を滴下し１５分攪拌した後、無水硫酸マグネシウムで乾燥させ、次いでセライト濾過し、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（ジクロロメタン：メタノール＝１５：１）で精製した（無色油状、収量８２６．６ｍｇ、収率８６．１％）。
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，Ｃ₆Ｄ₆）δ／ｐｐｍ ７．４３（ｄｄ，６Ｈ，Ｊ＝７．７，７．０Ｈｚ），６．９０（ｄ，６Ｈ，Ｊ＝８．２Ｈｚ），６．６６（ｄ，６Ｈ，Ｊ＝２．１Ｈｚ），６．５６（ｔ，３Ｈ，Ｊ＝２．１Ｈｚ），４．７２（ｓ，６Ｈ），３．８１（ｔ，１２Ｈ，Ｊ＝４．９Ｈｚ），３．５５（ｔ，１２Ｈ，Ｊ＝４．９Ｈｚ），３．４８−３．４５（ｍ，８４Ｈ），３．３６−３．３４（ｍ，１２Ｈ），３．１３（ｓ，１８Ｈ）
³¹Ｐ−ＮＭＲ（２０２ＭＨｚ，Ｃ₆Ｄ₆）δ／ｐｐｍ −９．７
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

A deoxygenated anhydrous xylene solution (5 ml) containing 967.4 mg of a phosphine oxide-containing dendrimer represented by the formula: An oxygen-free xylene solution (1 ml) was sequentially added, and the mixture was stirred at room temperature for 20 minutes and then stirred at 110 ° C. for 14 hours to be reacted.
To the reaction solution thus obtained, an aqueous solution (1 ml) of 230 mg of sodium hydroxide was added dropwise at 0 ° C., stirred for 15 minutes, dried over anhydrous magnesium sulfate, filtered through Celite, and the filtrate was subjected to reduced pressure. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography (dichloromethane: methanol = 15: 1) (colorless oil, yield 826.6 mg, yield 86.1%).
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 7.43 (dd, 6H, J = 7.7, 7.0 Hz), 6.90 (d, 6H, J = 8.2 Hz), 6 .66 (d, 6H, J = 2.1 Hz), 6.56 (t, 3H, J = 2.1 Hz), 4.72 (s, 6H), 3.81 (t, 12H, J = 4. 9 Hz), 3.55 (t, 12H, J = 4.9 Hz), 3.48-3.45 (m, 84H), 3.36-3.34 (m, 12H), 3.13 (s, 18H)
³¹ P-NMR (202 MHz, C ₆ D ₆ ) δ / ppm −9.7
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるホスフィン内包型デンドリマー５１８．８ｍｇの無水テトラヒドロフラン溶液（５ｍｌ）に、氷冷下水酸化カリウム３６１ｍｇの無水エタノール溶液（２ｍｌ）を加え、室温にて６．５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１時間おきにアルゴンにて脱気を行った水（１ｍｌ）を４回、計４ｍｌ加えた。
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（５０ｍｌ）に滴下して目的生成物を沈降させ、これを濾別し、４０℃で１６時間真空乾燥した（白色粉体、４１０．５ｍｇ、収率８３．７％）。
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，ＣＤ₃ＳＯＣＤ₃）δ／ｐｐｍ ８．００（ｄ，１２Ｈ，Ｊ＝８．２Ｈｚ），７．５９（ｄ，１２Ｈ，Ｊ＝８．２Ｈｚ），７．１９（ｔ，６Ｈ，Ｊ＝８．２Ｈｚ），７．０６（ｄ，６Ｈ，Ｊ＝８．２Ｈｚ），６．７７（ｓ，６Ｈ），６．７１（ｓ，３Ｈ），５．２２（ｓ，１２Ｈ），５．０７（ｓ，６Ｈ）
³¹Ｐ−ＮＭＲ（２０２ＭＨｚ，ＣＤ₃ＳＯＣＤ₃）δ／ｐｐｍ −１０．８
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 an anhydrous tetrahydrofuran solution (5 ml) containing 518.8 mg of the phosphine-containing dendrimer represented by the formula, an absolute ethanol solution (2 ml) of 361 mg of potassium hydroxide was added under ice cooling, and the mixture was stirred at room temperature for 6.5 hours. In order to dissolve the produced carboxylate, 4 ml of water (1 ml) degassed with argon every 1 hour after the start of the reaction was added four times.
After the reaction, the reaction solution was evaporated under reduced pressure, and the resulting oily substance was added dropwise to 1 mol / l hydrochloric acid (50 ml) to precipitate the desired product, which was filtered off and vacuumed at 40 ° C. for 16 hours. Dried (white powder, 410.5 mg, 83.7% yield).
The results of nuclear magnetic resonance spectrum analysis of this product are as follows.
¹ H-NMR (500 MHz, CD ₃ SOCD ₃ ) δ / ppm 8.00 (d, 12 H, J = 8.2 Hz), 7.59 (d, 12 H, J = 8.2 Hz), 7.19 (t , 6H, J = 8.2 Hz), 7.06 (d, 6H, J = 8.2 Hz), 6.77 (s, 6H), 6.71 (s, 3H), 5.22 (s, 12H) ), 5.07 (s, 6H)
³¹ P-NMR (202 MHz, CD ₃ SOCD ₃ ) δ / ppm −10.8
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 (allyl) di-μ-chlorodipalladium (II) [PdClC _3] was added to a deoxygenated anhydrous benzene solution (1 ml) containing 41.0 mg of the phosphine-containing dendrimer obtained in Example 1 at 0 ° C. H ₅ ] ₂ 5.2 mg was added, and the mixture was stirred at room temperature for 1 hour to be reacted.
The reaction solution thus obtained was evaporated under reduced pressure and dried in vacuo at 30 ° C. for 1 hour to obtain 48.5 mg of the desired product.
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, C ₆ D ₆ ) δ / ppm 7.75 (t, 6H, J = 8.8 Hz), 6.89 (d, 6H, J = 8.8 Hz), 6.64 (d , 6H, J = 1.8 Hz), 6.52 (s, 6H), 5.08-4.98 (m, 1H), 4.69 (s, 6H), 3.79 (t, 12H, J = 4.7 Hz), 3.53 (t, 12 H, J = 4.9 Hz), 3.50-3.45 (m, 38 H), 3.34 (t, 12 H, J = 4.7 Hz), 3 .12 (s, 18H), 2.43 (bs, 2H)
³¹ P-NMR (202 MHz, C ₆ D ₆ ) δ / ppm 18.9
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２−フェニル−１，３，２−ジオキサボリナン９７６ｍｇ、及び炭酸カリウム２．５０３ｇを順次加え、６０℃にて３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）で分離、精製して以下の構造式

で表わされる炭化水素６６４ｍｇ（収率８４．８％）を得た。 Under an argon atmosphere, bis (allyl) di-μ-chlorodipalladium (II) [PdClC ₃ ] was added at 0 ° C. to 74.8 mg of the phosphine-encapsulated dendrimer obtained in Example 1 (2.5 ml). 7.2 mg of H ₅ ] ₂ was added, and the mixture was stirred at room temperature for 40 minutes to prepare a palladium (II) phosphine complex catalyst-containing solution composed of a palladium-containing compound of the formula (XX). In this solution, cinnamil acetate 710 mg, the following structural formula

976 mg of 2-phenyl-1,3,2-dioxaborinane and 2.503 g of potassium carbonate were sequentially added, and the mixture was stirred at 60 ° C. for 3 hours to be reacted.
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) to obtain the following structural formula.

664 mg (yield 84.8%) of the hydrocarbon represented by

Claims (5)

Formula (I)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

( Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0 , n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
Is a group represented by
A phosphine-encapsulated amphiphilic dendrimer characterized by being represented by the formula: Formula (III)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ′ is represented by the general formula (IV)

( Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a bivalent linking group comprising a carbonyl group, p is 1, q, r, s and t are each 0 , n is an integer of 1 or more, k is an integer of 1 or more, and at least two of d, e and f are 1 And the rest indicate 0)
Is a group represented by
A phosphine oxide-encapsulated dendrimer represented by the general formula (V):

(Wherein u, v and G ′ are as described above)
The manufacturing method of the phosphine inclusion type amphiphilic dendrimer represented by these. Formula (VI)

[Wherein u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G ″ is represented by the general formula (VII)

( Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , R ⁵ is a hydrocarbon group, Y and Z are O, S, A divalent linking group comprising SO, SO ₂ , an amide group or a carbonyl group, p is 1, q, r, s and t are each 0 , n is an integer of 1 or more, m is an integer of 0 or more, d, e and (At least two of f indicate 1 and the rest indicate 0)
Is a group represented by
The phosphine-encapsulated dendrimer represented by the general formula (VIII) is hydrolyzed with lithium hydroxide, sodium hydroxide or potassium hydroxide in a solvent and optionally further reacted with an acid.

[Wherein u and v are 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 phosphine inclusion type amphiphilic dendrimer represented by these.   A phosphine ligand comprising the phosphine-encapsulated amphiphilic dendrimer according to claim 1. The general formula (X) having a coordination structure containing the phosphine ligand according to claim 4

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

( Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0 , n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
L ¹ is a halide ion, nitrate ion or acetate ion, and g is 1 or 2.]
And general formula (XI)

[Wherein, u is an integer of 0 to 2, v is an integer of 1 to 3, and u + v = 3, and G is represented by the general formula (II)

( Wherein R ¹ , R ² and R ³ are alkylene groups having 1 to 10 carbon atoms, R ⁴ is CH ₂ or CH ₂ C ₆ H ₄ , Y and Z are O, S, SO, SO ₂ and amide groups. Or a divalent linking group consisting of a carbonyl group, X is a hydrogen atom, carboxyl group, lithium carboxylate group, sodium carboxylate group or potassium carboxylate group, p is 1, q, r, s and t are 0 , n is At least two of integers of 1 or more, d, e, and f are 1 and the remaining are 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. is there)
L ² and L ³ are different from each other and represent a halide ion, a nitrate ion, an acetate ion or an allyl anion, and h represents 1 or 2, but either L ² or L ³ is allyl. In the case of an anion, h represents 1]
A palladium-containing complex catalyst comprising at least one selected from the amphiphilic dendrimer-fixed palladium (II) phosphine complexes represented by the formula: