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A method for palladium-catalyzed asymmetric hydrogenation of 1,3-diketones to synthesize β-hydroxy ketones

An asymmetric, palladium-catalyzed technology, applied in chemical instruments and methods, preparation of organic compounds, catalytic reactions, etc., to achieve the effects of convenient preparation, mild reaction conditions, and simple and practical reaction operations

Active Publication Date: 2021-10-08
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 1981, the Japanese scientist Yoshikawa group reported for the first time that Ru 2 Cl 4 (DIOP) 3 As a catalyst, asymmetric hydrogenation and desymmetry of cyclic anhydrides can be used to obtain stable lactone compounds, but only 20% enantioselectivity

Method used

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  • A method for palladium-catalyzed asymmetric hydrogenation of 1,3-diketones to synthesize β-hydroxy ketones
  • A method for palladium-catalyzed asymmetric hydrogenation of 1,3-diketones to synthesize β-hydroxy ketones
  • A method for palladium-catalyzed asymmetric hydrogenation of 1,3-diketones to synthesize β-hydroxy ketones

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Optimization of hydrogenation reaction conditions

[0029] Under a nitrogen atmosphere, put the palladium precursor (1mol%-5mol% of the substrate amount) and the chiral bisphosphine ligand (1mol%-12mol% of the substrate amount) into the reaction flask, add acetone (1.0-2.0mL) After stirring at room temperature for 1 h, the acetone was removed under reduced pressure, and then the catalyst was brought into the glove box, and the catalyst was dissolved with trifluoroethanol and dichloromethane as solvents used for hydrogenation reaction, and transferred to a medium containing acid additive (1.0-2.0% of the amount of substrate used). equiv.) and substrate 0.2mmol), then put the reaction bottle into the reaction kettle, feed hydrogen (100psi-1000psi), and react for 12-150 hours at 0-80°C; release hydrogen, reduce Remove the solvent under pressure, add aqueous sodium bicarbonate, extract with DCM, combine the organic layers, remove the solvent under reduced pressure, and sepa...

Embodiment 2

[0036] Synthesis of Chiral β-Hydroxyketone 2 by Hydrogenation Desymmetry of 1,3-Diketone 1

[0037] Under a nitrogen atmosphere, put the palladium precursor (1mol%-5mol% of the substrate amount) and the chiral bisphosphine ligand (1mol%-12mol% of the substrate amount) into the reaction flask, add acetone (1.0-2.0mL) After stirring at room temperature for 1 h, the acetone was removed under reduced pressure, and then the catalyst was brought into the glove box, and the catalyst was dissolved with the solvent used in the hydrogenation reaction, and transferred to a solvent containing additive (1.0-2.0 equiv. of substrate dosage) and substrate 0.2mmol ) into the reaction bottle, and then put the reaction bottle into the reaction kettle, pass in hydrogen gas (100psi-1000psi), react at 0-80°C for 12-150h hours; release hydrogen gas, remove the solvent under reduced pressure, add sodium bicarbonate Aqueous solution, DCM extraction, combine the organic layers, remove the solvent under...

Embodiment 3

[0041] Synthesis of Chiral β-Hydroxyketone 4 by Hydrogenation Desymmetry of 1,3-Diketone 3

[0042] Under a nitrogen atmosphere, put the palladium precursor (1mol%-5mol% of the substrate amount) and the chiral bisphosphine ligand (1mol%-12mol% of the substrate amount) into the reaction flask, add acetone (1.0-2.0mL) After stirring at room temperature for 1 h, the acetone was removed under reduced pressure, and then the catalyst was brought into the glove box, and the catalyst was dissolved with the solvent used in the hydrogenation reaction, and transferred to a solvent containing additive (1.0-2.0 equiv. of substrate dosage) and substrate 0.2mmol ) into the reaction bottle, and then put the reaction bottle into the reaction kettle, pass in hydrogen (100psi-1000psi), react at 0-80°C for 12-150 hours; release hydrogen, remove the solvent under reduced pressure, add sodium bicarbonate Aqueous solution, DCM extraction, combine organic layer, remove solvent under reduced pressure,...

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Abstract

A method for synthesizing chiral β-hydroxy ketones by desymmetrizing 1,3-diketones through palladium-catalyzed hydrogenation. Using 1-5mol% palladium catalyst and adding 10-100mol% acid to carry out asymmetric hydrogenation desymmetrization of 2-substituted 1,3-diketone compounds. The corresponding chiral β-hydroxy ketone compounds are obtained with an enantiomeric excess of up to 98%. The invention has the advantages of simple and practical operation, high yield, environmental friendliness, commercially available catalyst, mild reaction conditions and potential practical application value.

Description

technical field [0001] The invention belongs to the field of asymmetric hydrogenation synthesis, and in particular relates to a method for synthesizing chiral β-hydroxy ketones through the hydrogenation desymmetry reaction of 2-substituted 1,3-diketones catalyzed by a homogeneous palladium system with high enantioselectivity. Background technique [0002] Optically active β-hydroxy ketone compounds can be conveniently constructed into a series of biologically active organic molecules by further halogenation, hydrogenation, amination, etc. due to their diverse functional groups. (Reference 1: (a) Davis, F.A.; Chen, B.-C. Chem. Rev. 1992, 92, 919. (b) Adam, W.; Lazarus, M.; C.R.; Schreier, P.Acc.Chem.Res.1999, 32, 837.) Such as Calcitriol (calcitriol), which is the main ingredient of vitamin D sold on the market. And 2-methyl-2-allyl-3-hydroxycyclopentanone is the key starting material for the synthesis of natural products Coriolin and Anguidine. (References 2: (a) Attwood,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C45/64C07C49/747C07C49/755C07C49/83C07D307/93C07D311/94B01J31/24
CPCB01J31/2409B01J31/2452B01J31/2457B01J2231/643B01J2531/0213B01J2531/824C07C45/64C07D307/93C07D311/94C07C2601/08C07C2602/08C07C2603/28C07C2603/94C07C49/747C07C49/755C07C49/83
Inventor 余长斌周永贵李翔孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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