Chiral diphosphine ligand and chiral catalyst, and preparation and application method thereof

A technology of chiral bisphosphine ligands and chiral catalysts, which is applied in organic chemistry methods, chemical instruments and methods, and the preparation of organic compounds. It can solve problems that have not yet been seen, and achieve improved renewable performance and enhanced stability. , the effect of suppressing loss

Active Publication Date: 2013-04-24
山东聚强绿洲生物科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, no imidazole and imidazolium cation-modified BINAP chiral bisphosphine ligands and their application in ionic liquids have been reported.

Method used

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  • Chiral diphosphine ligand and chiral catalyst, and preparation and application method thereof
  • Chiral diphosphine ligand and chiral catalyst, and preparation and application method thereof
  • Chiral diphosphine ligand and chiral catalyst, and preparation and application method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1, the synthesis of chiral bisphosphine ligand precursor 4a and 4b

[0040](S)-5,5'-dibromo-2,2'-bisdiphenylphosphine oxide-1,1'-binaphthyl 3a (3.6g, 4.4mmol), imidazole (6.1g, 89.0mmol), K 2 CO 3 (2.5g, 18.0mmol), a mixture of CuI (0.35g, 1.8mmol) and L-proline (0.42g, 3.6mmol) was dissolved in 70mL of DMSO, and reacted at 140°C under an argon atmosphere for 48 Hour. After cooling, it was filtered, ethyl acetate was added to the filtrate, the organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residual solid was separated by silica gel column chromatography to obtain white solid 4a (1.7 g, 49.1%) and by-product 4b (0.78 g).

[0041] Characterization data for 4a: [α] 25 D : -187.3 (c0.5, DMF); 1 H NMR (500.0MHz, CDCl 3 ): δ=6.97(dd, J=8.5, 7.5Hz, 2H), 7.02(d, J=8.5Hz, 2H), 7.22-7.45(m, 22H), 7.50(dd, J=11.5, 9.0Hz, 2H), 7.62-7.69(m, 6H), 7.82(s, 2H); 13 C NMR ...

Embodiment 2

[0044] Embodiment 2, the synthesis of chiral bisphosphine ligand precursor 4c and 4d

[0045] Using (R)-5,5'-dibromo-2,2'-bisdiphenylphosphine oxide-1,1'-binaphthalene 3b as the starting material, the operation process is the same as in Example 1. The details are as follows: (R)-5,5'-dibromo-2,2'-bisdiphenylphosphine oxide-1,1'-binaphthyl 3b (3.6g, 4.4mmol), imidazole (6.1g, 89.0mmol ), K 2 CO 3 (2.5g, 18.0mmol), a mixture of CuI (0.35g, 1.8mmol) and L-proline (0.42g, 3.6mmol) was dissolved in 70mL of dimethyl sulfoxide, and reacted at 140°C under an argon atmosphere for 48 Hour. After cooling, it was filtered, ethyl acetate was added to the filtrate, the organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residual solid was separated by silica gel column chromatography to obtain white solid 4c (1.8 g) and by-product 4d (0.7 g).

[0046] Explanation: The main reason for using (R)-5...

Embodiment 3

[0047] Embodiment 3, the synthesis of chiral bisphosphine ligand 1a

[0048] Under an argon atmosphere, a mixture of 4a (0.2 g, 0.26 mmol) and phenylsilane (1.5 mL, 12.2 mmol) was heated to 130 °C, and three portions of trichlorosilane (3 × 0.4 mL) were heated for 1 h and 3 h, respectively. and 15 hours were added, and the reaction continued to stir for 2 hours. After cooling, the volatile components were removed under reduced pressure to obtain a white solid. Washing with cyclohexane, filtering, and evaporating the solvent gave the chiral bisphosphine ligand 1a in quantitative yield. [α] 20 D : -90.4(c0.5, DMF); 1 H NMR (500.0MHz, CDCl 3 ): δ=6.91(d, J=8.5Hz, 2H), 6.97(t, J=7.6Hz, 2H), 6.99-7.25(m, 20H), 7.36(d, J=7.0Hz, 2H), 7.40 (s, 2H), 7.47(s, 2H), 7.53(d, J=8.5Hz, 2H), 7.58(d, J=8.5Hz, 2H), 8.23(s, 2H); 13 CNMR (125.7MHz, CDCl 3 ): δ=121.8, 124.6, 125.2, 128.4, 128.5, 128.6, 129.1, 129.3, 132.3, 132.7, 132.8, 132.9, 133.8, 134.3, 134.4, 134.5, 135.7, 136.4, 138.7...

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Abstract

The invention relates to a chiral diphosphine ligand and a chiral catalyst, and a preparation and application method thereof. The preparation method of a BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) chiral diphosphine ligand based on novel imidazole and imidazole cation modification. Imidazole and imidazole cation are introduced to the 5,5'- position of the BINAP molecule framework to synthesize the chiral diphosphine ligand. The assembly of the imidazole and imidazole cation into the chiral diphosphine ligand molecule can effectively enhance the stability of the chiral catalyst in an ionic liquid and the affinity with the imidazole ionic liquid, and avoids loss of the catalyst in the cyclic process. The imidazole-modified chiral diphosphine ligand has the following chemical structural formula, wherein the spatial configuration of the imidazole-modified chiral diphosphine ligand is S type or R type.

Description

technical field [0001] The invention relates to imidazole, a chiral bisphosphine ligand modified by imidazolium cations, a chiral catalyst and a preparation method, and the application of ruthenium dibromine complexes in the asymmetric catalytic hydrogenation of β-ketoesters, belonging to organic compounds of chemical technology synthetic field. Background technique [0002] Chiral phosphine ligands are an important component of chiral transition metal catalysts. The core issue of asymmetric catalytic reactions is to prepare chiral catalysts with high activity and high stereoselectivity by designing and synthesizing chiral phosphine ligands and complexing with transition metals. So far, thousands of chiral phosphine ligands have been synthesized, which have C 2 Axisymmetric BINAP has strong chiral recognition ability and is widely used in various asymmetric catalytic reactions. For example, Ru-BINAP is currently recognized as an efficient catalyst for asymmetric hydrogena...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6506B01J31/22C07B53/00C07C69/675C07C69/732C07C67/31
CPCY02P20/50
Inventor 金欣杨志强
Owner 山东聚强绿洲生物科技有限公司
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