JP2000119285A - New optically active aryloxyacyl platinum (ii) complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new optically active aryloxyacyl platinum (II) complex having an optical active nitrogen-phosphorus hetero-bidentate ligand, acting as a catalyst or a catalyst precursor in various synthetic reactions to give a practical reaction yield and giving an excellent asymmetric yield in an asymmetric synthesizing reaction. SOLUTION: This compound is expressed by formula I (R1 to R4 are each H, a halogen, an alkyl or the like; L is an optical active nitrogen-phosphorus hetero-bidentate ligand), for example, the compound of formula II. The compound of formula I is obtained, for example, by reaction potassium tetrachloro platinate and salicyl aldehyde having corresponding substituent in dimethylsulfoxide, and then reacting with the optical active nitrogen-phosphorus hetero-bidentate ligand corresponding to L. The objective compound is capable of obtaining a hydrosililated compound in a practical yield without activation in carrying out hydrosililating reaction of an olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a nitrogen-phosphorus heterocycle which can give a practical reaction yield as a catalyst or a catalyst precursor for various synthesis reactions and can give a good asymmetric yield in an asymmetric synthesis reaction. The present invention relates to a novel optically active aryloxyacylplatinum (II) complex having a bidentate ligand.

[0002]

2. Description of the Related Art As an optically active aryloxyacylplatinum (II) complex, one having a bisphosphine ligand as an optically active ligand is known [Organo].
metallics, 13, 3442 (1994)].
However, since this complex is a stable compound that can be synthesized in one step from commercially available potassium tetrachloroplatinate, it cannot be used as a catalyst for a synthesis reaction without any activation treatment. That is, a complex that acts as a catalyst for a synthesis reaction without an activation treatment is not known. For this reason, for example, this complex is used as a catalyst in an asymmetric oxidation reaction after being activated with perchloric acid under an inert gas atmosphere, but both the reaction yield and the asymmetric yield are at practical levels. Has not been reached. Further, application of such a complex to other reactions has hardly been studied.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a practical reaction yield by acting as a catalyst without performing an activation treatment in various synthetic reactions, and provides a good asymmetric synthesis in an asymmetric synthesis reaction. It is an object of the present invention to provide a novel optically active aryloxyacylplatinum (II) complex that can give a yield. In addition, in various synthesis reactions, when acting as a catalyst precursor (that is, acting as a catalyst after performing an activation treatment), a practical reaction yield is obtained, and further, in the case of an asymmetric synthesis reaction, good. Asymmetric yields,
It is an object to provide a novel optically active aryloxyacylplatinum (II) complex.

[0004]

The object of the present invention is achieved by a novel optically active aryloxyacylplatinum (II) complex having a nitrogen-phosphorus heterobidentate ligand represented by the formula (1).

[0005]

Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, or a dialkylamino group. And each may be the same or different, and two adjacent groups may be bonded to each other to form a ring. L represents an optically active nitrogen-phosphorus heterobidentate ligand.)

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The novel optically active aryloxyacylplatinum (II) complex of the present invention is a compound represented by the above formula (1). For example, potassium tetrachloroplatinate is converted to a corresponding compound in dimethyl sulfoxide. By reacting with a salicylaldehyde having a substituent represented by formula (1) and then with an optically active nitrogen-phosphorus heterobidentate ligand corresponding to L.

In the formula (1), when R ^{1 to} R ⁴ are halogen atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When R ^{1 to} R ⁴ are an alkyl group, the alkyl group has 1 to 2 carbon atoms.
0, preferably 1 to 12 acyclic alkyl groups (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl) And cycloalkyl groups having 3 to 7 carbon atoms (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.). When R ^{1 to} R ⁴ are alkenyl groups, the alkenyl group may be an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms (vinyl group, propenyl group,
Butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc.). Also, R ^1-
When R ⁴ is an aryl group, the aryl group has 6 carbon atoms.
To 20, preferably 6 to 12 aryl groups (phenyl group, tolyl group, xylyl group, naphthyl group, dimethylnaphthyl group, etc.).

In the formula (1), when R ^{1 to} R ⁴ are an alkoxy group, the alkoxy group may be an alkoxy group having 1 to 10 carbon atoms (a methoxy group, an ethoxy group, a propoxy group,
Butoxy group, pentoxy group, etc.). R ^{1 to} R ⁴
Is an aryloxy group, the aryloxy group includes an aryloxy group having 6 to 14 carbon atoms (a phenoxy group, a troxy group, a xyloxy group, a naphthoxy group, etc.)
Is mentioned. When R ^{1 to} R ⁴ are dialkylamino groups, examples of the dialkylamino group include dialkylamino groups having 2 to 10 carbon atoms (dimethylamino group, diethylamino group, and the like). In addition, these alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, and dialkylamino group are n-, i-, s-, and t.
-, O-, m-, p-, α-, β- and various isomers.

When R ^{1 to} R ⁴ are the aforementioned alkyl, alkenyl, aryl, alkoxy, aryloxy or dialkylamino groups, adjacent groups (ie, R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ ) may be linked to form a ring (such as a benzene ring or a cycloalkane ring having 4 to 8 carbon atoms such as cyclopentane and cyclohexane). At this time, the formed ring may contain a hetero atom such as an oxygen atom or a nitrogen atom.

In the formula (1), examples of the optically active nitrogen-phosphorus heterobidentate ligand represented by L include a compound represented by the formula (2)
-A), (2-b), (3-a), (3-b), (4-
a) and the compound represented by any of (4-b).

[0011]

Embedded image (Wherein, R ⁵ and R ⁶ are substituents on an aromatic ring or a heteroaromatic ring, and represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R ⁷ represents an alkyl group or an aryl group; R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, or a dialkylamino group. Represents an integer, provided that R ⁸ and R ⁹
R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ may be the same. )

In the optically active nitrogen-phosphorus heterobidentate ligand, the alkyl group and the aryl group represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are as described above. R ¹
It includes the same groups as alkyl and aryl groups represented by to R ^4. The halogen atoms represented by R ⁵ and R ⁶ are the same as described above. When R ⁵ and R ⁶ are a halogen atom, an acyclic alkyl group, a cyclic alkyl group, or an aryl group, the number of R ⁵ and R ⁶ on the aromatic ring or the heteroaromatic ring is one or two. Is preferred.

In the substituents represented by R ^{5 to} R ¹⁰ , the hydrogen atom bonded to the carbon atom is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, It may be further substituted with a dialkylamino group, a halogen atom or the like. These substituents are the same as those described above and represented by R ^{1 to} R ⁴ . In addition, in the substituents represented by R ^{5 to} R ¹⁰ , a hydrogen atom bonded to the carbon atom has 1 to 6 carbon atoms.
An alkyl or arylthio group (methylthio group, ethylthio group, propylthio group, butylthio group, phenylthio group, etc.), an alkoxycarbonyl group having 2 to 10 carbon atoms (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), a hydroxyl group, or A siloxy group having 3 to 24 carbon atoms (trimethylsiloxy group, triethylsiloxy group, tri-i-propylsiloxy group, tributylsiloxy group, i-propyldimethylsiloxy group, methyldi-i
-Propylsiloxy group, t-butyldimethylsiloxy group, methyldi-t-butylsiloxy group, tribenzylsiloxy group, tri-p-xylylsiloxy group, t-butyldiphenylsiloxy group, triphenylmethyldimethylsiloxy group, etc.) May be substituted.

Examples of the optically active nitrogen-phosphorus heterobidentate ligand (L) include the following compounds (R
Body, S body). Formulas (2-a) and (2-b)
, A compound (QUINAP) in which R ⁷ is a phenyl group and R ⁵ and R ⁶ are hydrogen atoms is exemplified.

In the formulas (3-a) and (3-b),
A compound (DPMO) in which R ⁷ is a phenyl group, R ⁸ is a methyl group and R ⁵ , R ⁹ , and R ¹⁰ are hydrogen atoms, or a compound in which R ⁷ is a phenyl group, R ⁸ is an i-propyl group, and R ⁵ , A compound in which R ⁹ and R ¹⁰ are hydrogen atoms (DPIPO), R ⁷ is a phenyl group,
A compound (DPIBO) in which R ⁸ is an i-butyl group and R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms, or a compound in which R ⁷ is a phenyl group and R ⁸ is t
A compound in which R ⁵ , R ⁹ , and R ¹⁰ are hydrogen atoms (DPTBO), or R ⁷ is a phenyl group, R ⁸ is a benzyl group, and R ⁵ , R ⁹ , and R ¹⁰ are hydrogen atoms. Compound (DPBN
O), a compound (DPPO) in which R ⁷ and R ⁸ are phenyl groups and R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms, and a compound in which R ⁷ is a phenyl group and R ⁸ is a hydroxymethyl group, and R ⁵ , Compound in which R ⁹ is a hydrogen atom and R ¹⁰ is a phenyl group (DPHMPO)
A compound in which R ⁷ is a phenyl group, R ⁸ is a 1-methyl-1-hydroxyethyl group, and R ⁵ , R ⁹ , and R ¹⁰ are hydrogen atoms (DPMHEO), or a compound in which R ⁷ is a phenyl group and R ⁸ is A 1-methyl-1-tetrahydropyranoxyethyl group, R ⁵ ,
Compounds in which R ⁹ and R ¹⁰ are hydrogen atoms (DPTHPEO)
Or a compound (DPHPMO) in which R ⁷ is a phenyl group, R ⁸ is a 1-hydroxy-1-phenylmethyl group, and R ⁵ , R ⁹ , and R ¹⁰ are hydrogen atoms, or a compound in which R ⁷ is a phenyl group and R ⁸ is 1-tetrahydropyranoxy-1-phenylmethyl group,
Compounds in which R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms (DPTHPM
O) or R ⁷ is a phenyl group and R ⁸ is 1-benzyloxy-1
A compound in which R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms (DPBNPMO), R ⁷ is a phenyl group, R ⁸
Is a 1-hexyl-1-t-butyldimethylsiloxyheptyl group and R ⁵ , R ⁹ and R ¹⁰ are hydrogen atoms (D
PBHO) and the like. These compounds can be prepared by a known method [Tetrahedron, 52, 7547].
(1996)].

In the formulas (4-a) and (4-b), R ⁷ is a phenyl group, R ⁸ is a methyl group, and R ⁹ and R ¹⁰
Is a hydrogen atom and n = 0 (DPMMO),
R ⁷ is a phenyl group, R ⁸ is an i-propyl group, and R ⁹ and R ¹⁰
Is a hydrogen atom and n = 0 (DPMIPO)
And R ⁷ is a phenyl group, R ⁸ is an i-butyl group, and R ⁹ and R
Compound in which ¹⁰ is a hydrogen atom and n = 0 (DPMIBO)
And R ⁷ is a phenyl group, R ⁸ is a t-butyl group, and R ⁹ and R
Compound in which ¹⁰ is a hydrogen atom and n = 0 (DPMTBO)
Or a compound (DPMPO) in which R ⁷ and R ⁸ are phenyl groups, R ⁹ and R ¹⁰ are hydrogen atoms and n = 0, or a compound in which R ⁷ is a phenyl group, R ⁸ is a benzyl group, and R ⁹ and R ¹⁰ is a hydrogen atom,
and a compound in which n = 0 (DPMBNO). These compounds can be prepared by a known method [Tetrah
edron Letters, 34, 1769 (199
3) etc.].

As a specific example of the novel optically active aryloxyacylplatinum (II) complex of the present invention represented by the formula (1), for example, when L is (S) -DPIPO and R is
^A compound in which ^{1 to} R ⁴ are hydrogen atoms (shown by the formula 1a);
Is (S) -DPIPO, a compound in which R ¹ and R ³ are t-butyl groups, and R ² and R ⁴ are hydrogen atoms (shown by Formula 1b)
Or a compound in which L is (S) -DPTBO and R ^{1 to} R ⁴ are hydrogen atoms (shown by formula 1c), or a compound in which L is (S) -D
PTBO, wherein R ¹ and R ³ are a t-butyl group, R ² and R ⁴
Is a hydrogen atom (shown by Formula 1d), a compound in which L is (R) -DPPO and R ^{1 to} R ⁴ are hydrogen atoms (shown by Formula 1e), or a compound in which L is (R)- DPPO includes compounds in which R ¹ and R ³ are t-butyl groups and R ² and R ⁴ are hydrogen atoms (indicated by formula 1f). Also,
A compound in which L is (S) -QUINAP and R ^{1 to} R ⁴ are hydrogen atoms (shown by the formula 1g), or L is (S) -QUA
INAP wherein R ¹ and R ³ are a t-butyl group, R ² and R ⁴
Is a hydrogen atom (shown by Formula 1h), a compound in which L is (S) -DPBHO and R ^{1 to} R ⁴ are hydrogen atoms (shown by Formula 1i), and the like.

[0018]

Embedded image

The novel optically active aryloxyacylplatinum (II) complex of the present invention acts as a catalyst or a catalyst precursor in various synthetic reactions to give a practical reaction yield, and furthermore, in asymmetric synthetic reactions, It can give a good asymmetric yield. For example, in an olefin hydrosilylation reaction, a hydrosilylation product can be obtained with a practical reaction yield without performing an activation treatment. Also,
In the aldol reaction between ketene silyl acetal and an aldehyde, an activation treatment is performed, and then an optically active β-hydroxy ester derivative (an optically active β-hydroxy ester in which a hydroxyl group is protected by a silyl group) has a practical reaction yield. And a good asymmetric yield.

In the aldol reaction, the novel optically active aryloxyacylplatinum (II) complex of the present invention is preferably used as a catalyst after the activation treatment. This activation is performed by treating the optically active aryloxyacylplatinum (II) complex with a super strong acid in an oxygen (O ₂ ) atmosphere. At this time, the oxygen concentration in the processing atmosphere is not more than 100% by volume and is not particularly limited as long as oxygen is present. For example, 0.01 to 100% by volume, further 1 to 100% by volume, particularly 15 to 25% by volume % Is preferable. The processing temperature is -78 ° C.
To 140 ° C, more preferably 0 to 30 ° C.
The treatment atmosphere can be an oxygen atmosphere by using pure oxygen, air, or pure oxygen diluted with an inert gas (such as nitrogen), and the pressure is not particularly limited. In addition,
The activation treatment is usually performed in a system in which a solvent is present.

As the above-mentioned superacid, at least one of trifluoromethanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and perchloric acid is used. Among them, trifluoromethanesulfonic acid is preferable. The superacid is preferably used in an amount of 1 to 20 equivalents, more preferably 1 to 4 equivalents, per equivalent of the optically active aryloxyacylplatinum (II) complex.

In the above-mentioned treatment under an oxygen atmosphere, it is more preferable to carry out the treatment in the presence of water, since the rate can be increased. The amount of the water depends on the optically active bisphosphine aryloxyacylplatinum (II) complex 1.
It is preferably 1 to 20 equivalents, more preferably 2 to 4 equivalents, based on the equivalents. Water may be added to the solvent when performing the above treatment, or may be contained in the solvent in advance.

Examples of the solvent include aliphatic halogenated hydrocarbons (such as dichloromethane and dichloroethane), aromatic hydrocarbons (such as benzene, toluene and xylene), ethers (such as diisopropyl ether and tetrahydrofuran) and amides (such as dimethylformamide). , Sulfoxide (dimethyl sulfoxide and the like), nitrile (acetonitrile and the like) and the like, among which aliphatic halogenated hydrocarbons are preferable. These solvents are optically active bisphosphine aryloxyacylplatinum (II) complex 1 mmol
10-1000ml, and 50-500ml
Preferably it is used to a degree.

[0024]

The present invention will be specifically described below with reference to examples and comparative examples. Example 1 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of a)] In a Schlenk tube (100 ml volume), potassium tetrachloroplatinate (1.0 mmol), sodium carbonate (3.0 mmol), and salicylaldehyde (1.0 mm
ol) and dimethyl sulfoxide (16 ml) were added, and the mixture was stirred at 140 ° C for 40 minutes. Then, set the temperature to 100
After adding (S) -DPIPO (1.0 mmol) at a temperature of 60 ° C., the temperature was raised to 60 ° C., and dimethyl sulfoxide was distilled off under reduced pressure. From the obtained residue, methylene chloride extraction,
By recrystallization (solvent: methylene chloride-hexane), an optically active aryloxyacylplatinum (II) complex represented by the formula (1a); Pt (Sal) ｛(S) -DPIP
O｝ (0.59 g) was obtained (86% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.19-8.16 (m} , 1H), 7.6
1-7.11 (m, 15H), 6.84 (d, J = 8.
3,1H), 6.40 (dd, J = 7.3, 7.3, 1
H), 5.30-5.26 (m, 1H), 4.52-
4.43 (m, 2H), 2.66-2.63 (m, 1
H), 0.87 (d, J = 6.8, 3H), 0.35
(D, J = 6.8,3H), (2) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 14.5 (s, J _Pt-P = 4690), (3) Elemental analysis: Theoretical value (C ₃₁ H ₂₈ NO ₃ PPt) C: 54.07, H:
4.10, N: 2.03 measured value C: 53.57, H: 4.12, N: 2.00

Example 2 [Optically active aryloxyacylplatinum (II) complex (1
b) Synthesis of salicylaldehyde with 3,5-di-t-butyl-2-hydroxybenzaldehyde (1.0 mmol)
Except for replacing l), the reaction and isolation were carried out in the same manner as in Example 1 to obtain an optically active aryloxyacylplatinum (II) complex represented by the formula (1b); Pt (3,5-DTB)
S) {(S) -DPIPO} (0.55 g) was obtained (yield 69%). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.19-8.16 (m} , 1H), 7.5
9-7.26 (m, 13H), 7.14-7.07
(M, 2H), 5.28-5.23 (m, 1H), 4.
53-4.42 (m, 2H), 2.78-2.74
(M, 1H), 1.51 (s, 9H), 1.22 (s,
9H), 0.86 (d, J = 6.8, 3H), 0.25
(D, J = 6.8,3H), (2) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 15.0 (s, J _Pt-P = 4659), (3) Elemental analysis: Theoretical value (C ₃₉ H ₄₄ NO ₃ PPt) C: 58.49, H:
5.54, N: 1.75 Found C: 57.95, H: 5.78, N: 1.75

Example 3 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of c)] (S) -DPIPO is converted to (S) -DPTBO
(1.0 mmol), except that the reaction and isolation were performed in the same manner as in Example 1 to obtain an optically active aryloxyacylplatinum (II) complex represented by the formula (1c);
(Sal) {(S) -DPTBO} (0.52 g) was obtained (74% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.22-8.19 (m} , 1H), 7.6
0-7.37 (m, 11H), 7.28-7.22
(M, 2H), 7.16 (dd, J = 7.8, 7.8,
1H), 7.05 (dd, J = 9.3, 7.8, 1
H), 6.84 (d, J = 8.3, 1H), 6.39
(Dd, J = 6.4, 6.4, 1H), 5.11 (d
d, J = 9.3, 3.9, 1H), 4.60-4.52.
(M, 2H), 0.79 ( s, 9H), (2) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 15.7 (s, J _Pt-P = 4740), (3) Elemental analysis: Theoretical value (C ₃₂ H ₃₀ NO ₃ PPt) C: 54.70, H:
4.30, N: 1.99 Measurement value C: 53.69, H: 4.18, N: 2.01

Example 4 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of d)] (S) -DPIPO is converted to (S) -DPTBO
(1.0 mmol), and the reaction and isolation were carried out in the same manner as in Example 2 to obtain an optically active aryloxyacylplatinum (II) complex represented by the formula (1d);
(3,5-DTBS) {(S) -DPTBO} (0.5
9g) was obtained (yield 73%). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.25-8.22 (m} , 1H), 7.5
9-7.35 (m, 13H), 7.12 (d, J = 2.
4,1H), 7.03 (dd, J = 10.2, 10.
2,1H), 5.21 (dd, J = 9.3, 2.9, 1
H), 4.62 (dd, J = 8.8, 2.9, 1H),
4.51 (dd, J = 9.3, 8.8, 1H), 1.5
0 (s, 9H), 1.22 (s, 9H), 0.77
(S, 9H), (2 ) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 16.3 (s, J _Pt-P = 4685), (3) Elemental analysis: Theoretical value (C ₄₀ H ₄₆ NO ₃ PPt) C: 58.96, H:
5.69, N: 1.72 Measured value C: 58.70, H: 5.69, N: 1.69

Example 5 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of e)] (S) -DPIPO is converted to (R) -DPPO
(1.0 mmol), and the reaction and isolation were carried out in the same manner as in Example 1 to obtain the optically active aryloxyacylplatinum (II) complex represented by the formula (1e);
(Sal) {(R) -DPPO} (0.64 g) was obtained (88% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.24-8.21 (m} , 1H), 7.6
2-7.26 (m, 14H), 7.16-7.12
(M, 3H), 7.06-7.01 (m, 3H), 6.
86 (d, J = 7.8, 1H), 6.38-6.33
(M, 2H), 4.91 (dd, J = 9.8, 8.8,
1H), 4.60 (dd, J = 8.8, 4.9, 1
^{H), (2) 31 P} {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 15.3 (s, J _Pt-P = 4710), (3) Elemental analysis: Theoretical value (C ₃₄ H ₂₆ NO ₃ PPt) C: 56.51, H:
3.63, N: 1.94 found C: 55.81, H: 3.63, N: 1.95

Example 6 [Optically active aryloxyacylplatinum (II) complex (1
f) Synthesis] (S) -DPIPO is converted to (R) -DPPO
(1.0 mmol), and the reaction and isolation were carried out in the same manner as in Example 2 to obtain an optically active aryloxyacylplatinum (II) complex represented by the formula (1f);
(3,5-DTBS) {(R) -DPPO} (0.48
g) (57% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 8.28-8.25 (m} , 1H), 7.6
4-7.60 (m, 1H), 7.55-7.38 (m,
7H), 7.42-7.36 (m, 5H), 7.21-
7.06 (m, 6H), 6.97-6.90 (m, 1
H), 6.46 (dd, J = 9.8, 3.9, 1H),
4.91 (dd, J = 9.8, 8.3, 1H), 4.5
4 (dd, J = 8.3, 3.9, 1H), 1.45
(S, 9H), 1.18 ( s, 9H), (2) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 15.7 (s, J _Pt-P = 4660) (3) Elemental analysis: Theoretical value (C ₄₂ H ₄₂ NO ₃ PPt) C: 60.43, H:
5.07, N: 1.68 measured value C: 59.85, H: 5.00, N: 1.68.

Example 7 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of g)] (S) -DPIPO is converted to (S) -QUIINA
Except for replacing P (1.0 mmol), the reaction and isolation were carried out in the same manner as in Example 1 to obtain an optically active aryloxyacylplatinum (II) complex represented by the above formula (1 g);
(Sal) {(S) -QUINAP} (0.75 g) was obtained (99% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
Cl ₃ ) δ: 9.27 (d, J = 6, ₃ , 1H), 7.
93 (dd, J = 16.0, 8.8, 2H), 7.76
-7.73 (m, 2H), 7.63-7.43 (m, 8
H), 7.29-7.11 (m, 5H), 6.99.
(D, J = 8.3, 1H), 6.93-6.79 (m,
6H), 6.46 (dd, J = 6.8, 6.8, 1
^{H), (2) 31 P} {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 23.0 (s, J _Pt-P = 4790), (3) Elemental analysis: Theoretical value (C ₃₈ H ₂₆ NO ₂ PPt) C: 60.48, H:
3.47, N: 1.86 found C: 59.53, H: 3.90, N: 1.80.

Example 8 [Optically active aryloxyacylplatinum (II) complex (1
h) Synthesis] (S) -DPIPO is converted to (S) -QUIINA
Except for replacing P (1.0 mmol), the reaction and isolation were carried out in the same manner as in Example 2 to obtain the optically active aryloxyacylplatinum (II) complex represented by the formula (1h);
(3,5-DTBS) {(S) -QUINAP} (0.
79 g) (91% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
Cl ₃ ) δ: 9.61 (d, J = 6, 4, 1H), 7.
94-7.90 (m, 2H), 7.74-7.72
(M, 2H), 7.62-7.41 (m, 10H),
7.32 (d, J = 2.0, 1H), 7.21-7.1
7 (m, 2H), 7.07 (dd, J = 8.8, 8.
8, 1H), 6.93-6.84 (m, 4H), 6.8.
0 (d, J = 8.8, 1H), 1.60 (s, 9H),
1.24 (s, 9H), ( 2) 31 P {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 23.0 (s, J _Pt-P = 4765) (3) Elemental analysis: Theoretical value (C ₄₆ H ₄₂ NO ₂ PPt) C: 63.73, H:
4.88, N: 1.62 measured value C: 62.70, H: 5.08, N: 1.54

Example 9 [Optically active aryloxyacylplatinum (II) complex (1
Synthesis of i)] In a Schlenk tube (25 ml volume), potassium tetrachloroplatinate (0.5 mmol), sodium carbonate (1.5 mmol), salicylaldehyde (0.5 mm)
ol) and dimethyl sulfoxide (11 ml) were added, and the mixture was stirred at 140 ° C for 40 minutes. Then, set the temperature to 100
After adding (S) -DPBHO (0.5 mmol) at a temperature of 60 ° C., the temperature was raised to 60 ° C., and dimethyl sulfoxide was distilled off under reduced pressure. From the obtained residue, methylene chloride extraction,
By recrystallization (solvent: hexane), an optically active aryloxyacylplatinum (II) complex represented by the above formula (1i); Pt (Sal) {(S) -DPBHO} (0.29
g) (60% yield). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
Cl ₃ ) δ: 8.25 (dd, J = 6.8, 4.4, 1)
H), 7.64-7.36 (m, 12H), 7.23-
7.16 (m, 3H), 6.79 (d, J = 8.3, 1
H), 6.38 (dd, J = 7.8, 7.8, 1H),
5.56 (dd, J = 9.3, 3.9, 1H), 4.8
6 (dd, J = 8.3, 3.9, 1H), 4.55 (d
d, J = 9.3, 8.3, 1H), 2.10-0.94
(M, 20H), 0.88 (t, J = 7.3, 3H),
0.70 (t, J = 7.3, 3H), 0.55 (s, 9
H), 0.04 (s, 3H), -0.28 (s, 3
^{H), (2) 31 P} {1 H} -NMR (160MHz, CDC
l ₃ ) δ: 14.2 (s, J _Pt-P = 4770), (3) Elemental analysis: Theoretical value (C ₄₇ H ₆₂ NO ₄ PSiPt) C: 58.86,
H: 6.52, N: 1.46 measured value C: 58.22, H: 6.52, N: 1.54

Reference Example 1 [Hydrosilylation reaction] Schlenk tube (25 ml volume)
The optically active aryloxyacylplatinum (II)
Complex (1b) (6 mg; 0.0075 mmol) was weighed and styrene (312 mg; 3.0 mmol) was added. Then, phenyldimethylsilane (0.61 ml;
4 mmol) and stirred in air at room temperature for 1.5 hours. After completion of the reaction, the reaction solution was distilled under reduced pressure (5 torr).
r / bath temperature 210 ° C.) to give dimethylphenethylphenylsilane (720 mg) as a colorless oil (yield 99).
%). The analysis data is shown below.

(1) ¹ H-NMR (400 MHz, CD
_{Cl 3) δ: 7.44-7.40 (m} , 2H), 7.2
7-7.22 (m, 3H), 7.16-7.12 (m,
2H), 7.07-7.02 (m, 3H), 2.53
(T, J = 8.3, 2H), 1.04 (t, J = 8.3.
3,2H), 0.18 (s, 6H), (2) ¹³ C-NMR (100 MHz, CDCl ₃ ) δ:
145.0, 139.0, 133.6, 128.9, 1
28.3, 127.8, 127.7, 125.5, 2
9.9, 17.7, -3.1, (3) Mass spectrometry (EI) m / z (relative i
ntensity): 225 (M-CH 3 +, 5), 16
2 (50), 135 (100), 121 (600), 1
05 (30), 91 (17), 77 (10)

Reference Example 2 [Aldol reaction] The above-mentioned optically active aryloxyacylplatinum (II) complex (1d) (0.025 mmol) was weighed and placed in a Schlenk tube (25 ml), and water (0.05 mmol) was added.
5 mmol) in methylene chloride (2.5 ml) was added. At this time, the water concentration in methylene chloride was 300 pp.
m. Then, trifluoromethanesulfonic acid (0.025 mmol) was added, and the mixture was added in air at room temperature for 15 minutes.
After stirring for minutes, the complex was activated.

After the activation, 2,6-lutidine (0.025 mmol) was added to the reaction solution cooled to -78 ° C.
Then, hydrocinnamaldehyde (0.5 mmol) and methyltrimethylsilyldimethylketene acetal (0.7 mmol) were added dropwise. Thereafter, the system was replaced with an argon atmosphere, the temperature was set to -25 ° C, and an aldol reaction was performed. After 120 hours, the reaction was quenched at 0 ° C. using 1N hydrochloric acid, washed with water, treated with hydrochloric acid, extracted with methylene chloride, dried over magnesium sulfate, and subjected to column chromatography.
From the reaction solution, methyl 2,2-dimethyl-5-phenyl-3-trimethylsiloxypentanoate (153 mg) was separated as a colorless oily product (99% yield). The analysis data is shown below.

(1) IR (neat): 2955, 17
29,1251,1132,1101,840,75
1,699 (cm ^-1 ), (2) ¹ H-NMR (270 MHz, C ₆ D ₆ ) δ: 7.
18-7.03 (m, 5H), 4.06 (dd, J =
8.1, 2.9, 1H), 3.29 (s, 3H), 2.
88-2.78 (m, 1H), 2.55-2.37
(M, 1H), 1.75-1.60 (m, 2H), 1.
20 (s, 3H), 1.06 (s, 3H), 0.13
(S, 9H), (3) ¹³ C-NMR (67.5 MHz, C ₆ D ₆ ) δ: 1
77.0, 142.5, 128.7, 128.6, 12
6.2, 77.9, 51.2, 48.4, 35.4, 3
3.9, 21.3, 20.9, 0.9, (4) Mass spectrometry (CI) m / z (relative i
ntency): 309 (MH ⁺ , 40), 219
(98), 159 (45), 117 (100), 91
(96), 73 (70)

Further, the trimethylsilyl group of this product was deprotected with a tetrabutylammonium fluoride / tetrahydrofuran solution to obtain methyl 3-hydroxy-2,2-dimethyl-5-phenylpentanoate. Was determined by high performance liquid chromatography to find that 8
0% e. e. Met. The analysis conditions are shown below.

Column: ChiralPak-AD (manufactured by Daicel), Eluent: hexane / ethanol / trifluoroacetic acid = 9
7.5 volume parts / 2.5 volume parts / 0.1 volume parts; 0.8m
1 / min, Column temperature: 30 ° C, Detection: UV (220 nm)

Reference Example 3 [Aldol Reaction] The optically active aryloxyacylplatinum (II) complex (1d) was converted to the optically active aryloxyacylplatinum (II) complex (1i) (0.025 mmol).
The same operation as in Reference Example 2 was performed, except that l) was replaced.
As a result, the yield of methyl 2,2-dimethyl-5-phenyl-3-trimethylsiloxypentanoate was 99%, and the asymmetric yield was 84%.

[0050]

According to the present invention, in various synthetic reactions,
A novel optically active aryloxyacylplatinum (II) complex that can act as a catalyst without performing an activation treatment to give a practical reaction yield, and can also give a good asymmetric yield in an asymmetric synthesis reaction Can be provided. In addition, in various synthesis reactions, when acting as a catalyst precursor (that is, acting as a catalyst after performing an activation treatment), a practical reaction yield is obtained, and further, in the case of an asymmetric synthesis reaction, good. A novel optically active aryloxyacylplatinum (II) complex that can provide a high asymmetric yield can be provided. In particular, in the hydrosilylation reaction of an olefin, the corresponding hydrosilyl compound can be synthesized with a practical reaction yield without performing an activation treatment. In addition, in the reaction between ketene silyl acetal and aldehyde, after an activation treatment, asymmetric induction occurs at a very high rate, and the corresponding optically active β-hydroxy ester derivative (the hydroxyl group is protected by a silyl group). Optical activity β
-Hydroxyester) can be synthesized with a practical reaction yield and an asymmetric yield. In the hydrosilylation reaction of an olefin, the corresponding hydrosilyl compound can be synthesized with a practical reaction yield.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 24, 1999 (1999.5.2
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

In the above-mentioned treatment under an oxygen atmosphere, it is more preferable to carry out the treatment in the presence of water, since the rate can be increased. The amount of water is optically active A
1 to 1 equivalent of a reeloxyacylplatinum (II) complex
It is preferably from 20 to 20 equivalents, more preferably from 2 to 4 equivalents.
Water may be added to the solvent when performing the above treatment,
It may be contained in the solvent in advance.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

Examples of the solvent include aliphatic halogenated hydrocarbons (such as dichloromethane and dichloroethane), aromatic hydrocarbons (such as benzene, toluene and xylene), ethers (such as diisopropyl ether and tetrahydrofuran) and amides (such as dimethylformamide). , Sulfoxide (dimethyl sulfoxide and the like), nitrile (acetonitrile and the like) and the like, among which aliphatic halogenated hydrocarbons are preferable. These solvents are optically active aryl
10 to 10 mmol of xyacylplatinum (II) complex
It is preferable to use about 1000 ml, more preferably about 50 to 500 ml.

Continued on the front page F term (reference) 4C056 AA01 AB01 AC02 AD01 AE02 BA07 BC10 4H006 AA02 AC90 BA26 BA48 4H039 CA92 CF10 CF90 4H050 AA01 AB40 WB11 WB13 WB14 WB16 WB21

Claims (2)

[Claims] 1. A novel optically active aryloxyacylplatinum (II) complex having a nitrogen-phosphorus heterobidentate ligand represented by the formula (1). Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, or a dialkylamino group. And each may be the same or different, and two adjacent groups may be bonded to each other to form a ring. L represents an optically active nitrogen-phosphorus heterobidentate ligand.) 2. When L is represented by the formulas (2-a), (2-b), (3)
The novel optically active aryloxyacyl according to claim 1, which is an optically active nitrogen-phosphorus heterobidentate ligand represented by any one of -a), (3-b), (4-a) and (4-b). Platinum (II) complex. Embedded image (Wherein, R ⁵ and R ⁶ are substituents on an aromatic or heteroaromatic ring and represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R ⁷ represents an alkyl group or an aryl group; ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, or a dialkylamino group, and n is an integer of 0 to 10. With the proviso that R ⁸ and R ⁹
R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ may be the same. )