Ruthenium complexes having (p-p)-coordinated disphosphorus donor ligands and processes for preparing them

A technology of ruthenium complexes and ligands, applied in the field of ruthenium complexes for homogeneous catalysis, can solve the problems of high consumption of catalysts containing noble metals, long hydrogenation time, low enantioselectivity, etc.

Inactive Publication Date: 2013-04-10
UMICORE AG & CO KG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] Disadvantages of the catalytic hydrogenation processes described to date and of the catalysts used therein are in particular low reactivity, low enantioselectivity and high consumption of noble metal-containing catalysts, i.e. low "substrate / catalyst" (S / C) ratio
In addition, a longer hydrogenation time is required
Furthermore, many of the described complexes are difficult to synthesize, are air sensitive and are not very suitable for industrial applications

Method used

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  • Ruthenium complexes having (p-p)-coordinated disphosphorus donor ligands and processes for preparing them
  • Ruthenium complexes having (p-p)-coordinated disphosphorus donor ligands and processes for preparing them
  • Ruthenium complexes having (p-p)-coordinated disphosphorus donor ligands and processes for preparing them

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] (η5-2,4-dimethylpentadienyl) (CH 3 CN)-(Josiphos-SL-J212-1) Preparation of Ru(II) Tetrafluoroborate

[0079] a) (η 4-2,4-dimethylpentadienyl-η 2-C, H) (η 5-2,4-dimethylpentadienyl) ruthenium tetrafluoroborate

[0080] In a 100 ml Schlenk tube equipped with a magnetic stirrer, 1.1 g (3.77 mmol) of bis(η5-2,4-dimethylpentadienyl)ruthenium (UMICORE, Hanau) was dissolved in 50 ml of diethyl ether. Add 0.51ml (3.77mmol) of 54% HBF dropwise within 10 minutes at room temperature 4 -Et 2 O solution (from Aldrich). After the addition is complete, the mixture is allowed to settle, and the HBF is added dropwise by further 4 -Et 2 O to check whether the precipitation is complete. The upper solvent was removed, and the solid was washed twice with diethyl ether. The pale yellow residue was dried under reduced pressure. Yield 1.43 g (100%).

[0081] b) Acetonitrile complex (η5-2,4-dimethylpentadienyl) (CH 3 EN) 3 Preparation of ruthenium (II) tetrafluoroborate (starting com...

Embodiment 2

[0090] Preparation of (η5-2,4-dimethylpentadienyl)(iodo)-(Josiphos-SL-J212-1)ruthenium(II)

[0091] In a 25ml round bottom flask equipped with a magnetic stirrer, the acetonitrile complex (η5-2,4-dimethylpentadienyl) (SL-J212-1) ( CH 3 CN) Ruthenium(II) tetrafluoroborate (150 mg, 0.18 mmol) was dissolved in 4 ml acetone and 2 ml water and stirred with lithium iodide (LiI, 28.5 mg, 0.21 mmol) at room temperature for 3 hours. The solution was evaporated to dryness at room temperature under reduced pressure. The residue was washed three times with 1 ml of water. This gives the product in the form of a diastereomerically pure compound. Yield: 90%. pass 31 P-NMR spectroscopy verifies the P-P coordination of the SL-J-212-1.

[0092] Characterization:

[0093] 31 P NMR (CD 2 Cl 2 )δ: 7.51ppm (d, J PP =35.9Hz), 84.30ppm (d, J PP = 35.9Hz).

[0094] Use for catalytic hydrogenation

[0095] The (Josiphos-SL-J212-1)(iodo)ruthenium(II) complex prepared as described in Exampl...

Embodiment 3

[0097] (η5-2,4-dimethylpentadienyl) (CH 3 Preparation of CN)-((R,R)-DepyPhos) Ru(II) Tetrafluoroborate

[0098] In a 50 ml Schlenk test tube equipped with a magnetic stirrer, the acetonitrile complex (η5-2,4-dimethylpentadienyl) (CH 3 EN) 3 Ruthenium (II) tetrafluoroborate was dissolved in 15 ml of dichloromethane and stirred with 25 mg (0.05 mmol) of (R,R) DepyPhos (from Digital Speciallty Chemicals, Toronto, Canada) for half an hour at room temperature. Then 50 ml of n-hexane was added dropwise to the solution. A yellow-orange solid precipitated which was filtered off. Residual solvent was removed at room temperature under reduced pressure. The product was obtained in the form of diastereomerically pure compound, yield: 98%. pass 31 P NMR spectroscopy confirmed the P-P coordination of the ligand (thus the presence of a 5-membered ring).

[0099] Use for catalytic hydrogenation

[0100] The complex prepared as described in Example 3 was used for the asymmetric hydroge...

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Abstract

The invention relates to ruthenium complexes which have a chiral diphosphorus donor ligand and in which the ruthenium has the oxidation state (+11) and the chiral diphosphorus donor ligand has bidentate P-P coordination to the ruthenium. The ruthenium complexes are present in two forms (cationic type A and uncharged type B), are cyclic and have a four- to six-membered ring incorporating the diphosphorus donor ligand. The chiral diphosphorus donor ligands are selected from the group consisting of diphosphines, diphospholanes, diphosphites, diphosphonites and diazaphospholanes. Furthermore, processes for preparing the ruthenium complexes of types A and B, which are based on ligand exchange reactions, are described. The Ru complexes are used as catalysts for homogeneous asymmetric catalysis for preparing organic compounds.

Description

technical field [0001] The present invention relates to ruthenium complexes for homogeneous catalysis, in particular to P-P coordinated cyclic ruthenium complexes with chiral diphosphorus donor ligands. The invention also provides processes for their preparation, and the use of these complexes as catalysts for homogeneously catalyzed reactions, especially enantioselective hydrogenation reactions. Background technique [0002] Chiral diphosphorus donor ligands have been found to be valuable ligands for catalytically active metal complexes for use in homogeneously catalyzed reactions for the enantioselective hydrogenation of organic compounds. The field of application is the preparation of intermediates or active compounds, such as pharmaceuticals, pesticides, flavorings or fragrances. [0003] These diphosphorus donor ligands are used with suitable noble metal complexes in enantioselective hydrogenations. [0004] Organometallic Ru compounds used in these hydrogenation reac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00
CPCC07F17/02B01J31/185B01J31/1865B01J31/2409B01J2231/643B01J2231/645B01J2531/821C07B53/00C07C51/36C07C53/126
Inventor A·里瓦斯-纳斯R·卡希R·温德A·杜皮尤T·斯彻纳迪尔
Owner UMICORE AG & CO KG
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