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Chiral tetradentate ligand, chiral ruthenium complex and method for preparing (R)-(-)-1, 3-butanediol

A ruthenium complex and chiral technology is applied in the field of asymmetric hydrogenation of chiral ligands and the preparation of 1,3-butanediol, which can solve the problems of large amount of catalyst, difficult product separation and high cost, and achieves The reaction operation is simple, the raw materials are cheap and easy to obtain, and the preparation is simple.

Active Publication Date: 2021-03-23
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It solves the shortcomings of the existing technology for preparing (R)-(-)-1,3-butanediol, such as high cost, large amount of catalyst used, and difficult product separation, and can use low-cost, low-use catalyst to convert the substrate Asymmetric hydrogenation of the carbonyl group of methyl acetoacetate with simultaneous reduction of the ester group to give (R)-(-)-1,3-butanediol

Method used

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  • Chiral tetradentate ligand, chiral ruthenium complex and method for preparing (R)-(-)-1, 3-butanediol
  • Chiral tetradentate ligand, chiral ruthenium complex and method for preparing (R)-(-)-1, 3-butanediol
  • Chiral tetradentate ligand, chiral ruthenium complex and method for preparing (R)-(-)-1, 3-butanediol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] Example 1: Synthesis of chiral tetradentate phosphine nitrogen ligand L1

[0065] In the glove box, add (R)-1,1'-bi-2-naphthol (1g, 3.49mmol), DMAP (0.004g, 0.035mmol) and triethylamine (10g, 0.1mol) into a 50mL Schlenk bottle , It was sealed; Out of the glove box, put the Schlenk bottle into the water bath, start stirring, add phosphorus trichloride (0.48g, 3.49mmol) to the Schlenk bottle under argon atmosphere, and stir at room temperature for 1h. Continue to add triethanolamine dropwise to the Schlenk bottle under an argon atmosphere. After the dropwise addition, put the Schlenk bottle into an oil bath and heat to reflux for 2 to 3 hours. After the complete reaction of the raw material dinaphthol is monitored by TLC, the reaction is terminated. The reaction solution was cooled to room temperature, and the base was recovered by distillation under reduced pressure to obtain a crude tetradentate phosphine nitrogen ligand. The crude product was crystallized with a mixed...

Embodiment 2

[0066] Example 2: Synthesis of chiral tetradentate phosphine nitrogen ligand L2

[0067] In the glove box, add (R)-6,6'-dibromo-1,1'-bi-2-naphthol (0.5g, 1.125mmol), DAMP (1.4mg, 0.011mmol) and Triethylamine (10g) is sealed; out of the glove box, the Schlenk bottle is put into a water bath, and the stirring is started, and phosphorus trichloride (0.17g, 1.24mmol) is added to the Schlenk bottle under an argon atmosphere, and Stir for 1h. Continue to add triethanolamine (67mg, 0.45mmol) dropwise to the Schlenk bottle under the argon atmosphere. After the dropwise addition, the Schlenk bottle is put into the oil bath, and heated to reflux for 3h. After TLC monitors that the raw material dinaphthol has completely reacted, Stop the reaction. The reaction solution was cooled to room temperature, and the base was recovered by distillation under reduced pressure to obtain a crude tetradentate phosphine nitrogen ligand. The crude product was crystallized with a mixed solvent of dich...

Embodiment 3

[0068] Example 3: Synthesis of chiral tetradentate phosphine nitrogen ligand L3

[0069] In the glove box, add (R)-3,3'-di-tert-butyl-1,1'-bi-2-naphthol (0.2g, 0.50mmol), DAMP (0.61mg, 0.0050mmol) into a 10mL Schlenk bottle ) and triethylamine (6g), which are sealed; out of the glove box, the Schlenk bottle is put into a water bath, and the stirring is started, and phosphorus trichloride (76mg, 0.55mmol) is added to the Schlenk bottle under an argon atmosphere, and room temperature Stir for 1h. Continue to add triethanolamine (30mg, 0.20mmol) dropwise to the Schlenk bottle under an argon atmosphere. After the dropwise addition, the Schlenk bottle is put into an oil bath, and heated to reflux for 3h. After TLC monitors that the raw material dinaphthol has completely reacted, Stop the reaction. The reaction solution was cooled to room temperature, and the base was recovered by distillation under reduced pressure to obtain a crude tetradentate phosphine nitrogen ligand. The cr...

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Abstract

The invention discloses a chiral tetradentate ligand, a chiral ruthenium complex and a method for preparing (R)-(-)-1, 3-butanediol. The structural formula of the ligand is preferred, and R1 and R2 are H, Br, tert-butyl, phenyl, 3, 5-trifluoromethyl phenyl which are independent of each other. The method overcomes the defects of high cost, large catalyst dosage, difficulty in product separation andthe like in the existing technology for preparing (R)-(-)-1, 3-butanediol, and can perform asymmetric hydrogenation on carbonyl of the substrate methyl acetoacetate and reduce the ester group to obtain (R)-(-)-1, 3-butanediol by using a low-cost and small-dosage catalyst. The reaction operation process is simple, the catalyst is simple to prepare, and the yield and ee value of the target productare 98% or above. Meanwhile, the catalyst can be used for five times, so that the cost is greatly reduced, and the potential of industrial application is achieved.

Description

technical field [0001] The invention belongs to the field of catalysts and organic synthesis, and in particular relates to a chiral ligand for asymmetric hydrogenation and a method for preparing (R)-(-)-1,3-butanediol. Background technique [0002] (R)-(-)-1,3-Butanediol is an important chiral building block widely used in carbapenem antibiotic core azetidinones, spices, pheromones and insecticides Synthesis. Among them, carbapenem antibiotics can effectively alleviate the resistance to penicillin, so the synthesis of (R)-(-)-1,3-butanediol has received extensive attention at home and abroad. The synthesis methods include chemical methods and microbial methods. . [0003] Synthesis of (R)-(-)-1,3-butanediol by chemical method can be obtained by directly splitting racemic 1,3-butanediol. Condensation reaction and hydrogenation reaction to prepare racemic 1,3-butanediol, and then use a chiral resolving agent to resolve (R)-(-)-1,3-butanediol and (S)-(-) -1,3-butanediol, th...

Claims

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Application Information

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IPC IPC(8): C07F9/6574C07F15/00B01J31/18B01J31/22C07C29/149C07C31/20
CPCC07F9/65744C07F15/0053C07F15/0046B01J31/189B01J31/2213B01J31/2295C07C29/149C07B2200/07B01J2531/821B01J2531/0238B01J2531/0225B01J2531/0261B01J2231/641B01J2231/643C07C31/207
Inventor 沈稳王永军黄文学张永振黎源谢硕
Owner WANHUA CHEM GRP CO LTD
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