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Chiral ferrocene PNNO tetradentate ligand and application thereof in asymmetric hydrogenation reaction

A technology of chiral ferrocene and tetradentate ligands, applied in the field of fine chemical industry, can solve the problem of less research on tetradentate ligands, and achieve the effects of excellent stereoselectivity, high yield and easy modification

Active Publication Date: 2022-04-12
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The ferrocene skeleton is a very good ligand skeleton. Based on the ferrocene skeleton, chemists have developed a series of chiral ligands with excellent performance, such as bidentate ligands Josiphos, Taniaphos, Walphos, BoPhoz, Mandyphos, Trifer, ChenPhos, Fc-Phox, etc. Tridentate ligands Pigiphos, f-amphox, f-amphol, f-ampha, etc., but these ligands are mainly bidentate or tridentate ligands, containing ferrocene structural units The tetradentate ligands of

Method used

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  • Chiral ferrocene PNNO tetradentate ligand and application thereof in asymmetric hydrogenation reaction
  • Chiral ferrocene PNNO tetradentate ligand and application thereof in asymmetric hydrogenation reaction
  • Chiral ferrocene PNNO tetradentate ligand and application thereof in asymmetric hydrogenation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] Example 1: Synthesis of Key Fragment 3 (Compound 3) (R=Ph)

[0065]

[0066] Under nitrogen atmosphere and 0°C, 15mL of n-BuLi n-hexane solution (2.4mol / L, 36mmol) was added dropwise to 7.7g of compound 1 (30mmol, 1.0equiv.) in anhydrous ether (60mL) solution, dropwise After the addition was completed, it was naturally raised to room temperature and stirred for 2.0h. Ph 2 PCl (33mmol, 1.2equiv.) was dropped into the reaction solution, heated to reflux, monitored by TLC, quenched with water after the reaction was completed, extracted with ether to obtain an organic phase, dried with anhydrous sodium sulfate, filtered, and spin-dried to obtain a red oil The liquid was recrystallized to obtain 10.3 g of the product compound 2 with a yield of 78%.

[0067] Under nitrogen protection, a mixture of compound 2 (2 mmol) and acetic anhydride (2 mL) was heated at 100° C. for about 1˜2 h. After the reaction was completed, the acetic anhydride was removed under reduced pressur...

Embodiment 2

[0068] Example 2: Synthesis of key fragment 3 (compound 3) (R=3,5-di-tert-butylphenyl)

[0069]

[0070] Under nitrogen atmosphere and 0°C, 5 mL of n-BuLi n-hexane solution (2.4mol / L, 12mmol) was added dropwise to a solution of compound 1 (2.57g, 10mmol) in anhydrous ether (20mL). After the addition was complete, Naturally rose to room temperature and stirred for 2h. Then the temperature was lowered to -78°C, and redistilled PCl was slowly added dropwise. 3 (12 mmol, 1 mL), the mixture was warmed to room temperature and reacted overnight. Then the temperature was lowered to -78°C again, and RMgBr solution (25 mmol, newly prepared) was slowly added dropwise with a constant pressure funnel. After the dropwise addition, slowly warm up to room temperature overnight, then add 20 mL of saturated NH 4 Cl solution. The organic phase was extracted three times with ether, 20 mL of ether each time. The organic phase was dried with anhydrous sodium sulfate, spin-dried, and subject...

Embodiment 3

[0072] Embodiment 3: the synthesis of key segment 3 (compound 3) (R=cyclohexyl)

[0073]

[0074] Under nitrogen atmosphere and 0°C, 5 mL n-BuLi n-hexane solution (2.4 mol / L, 12 mmol) was added dropwise to 2.57 g (S)-1 (10 mmol, 1.0 equiv.) solution in anhydrous ether (20 mL) After the dropwise addition, it was naturally raised to room temperature and stirred for 2.0h. Cy 2 PCl (33mmol, 1.2equiv.) was added dropwise to the reaction solution, heated to reflux, monitored by TLC, quenched with water after the reaction was completed, extracted with ether to obtain an organic phase, dried with anhydrous sodium sulfate, filtered, and spin-dried to obtain a red oil Liquid, recrystallized to obtain 2.17g of yellow solid compound 2, yield 50%.

[0075]Under nitrogen protection, a mixture of compound 2 (2 mmol) and acetic anhydride (2 mL) was heated at 100° C. for about 1˜2 h. After the reaction was completed, the acetic anhydride was removed under reduced pressure to obtain compo...

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Abstract

The invention discloses a chiral ferrocene PNNO tetradentate ligand and application of the chiral ferrocene PNNO tetradentate ligand in asymmetric hydrogenation reaction, and belongs to the field of fine chemical engineering. The ligand disclosed by the invention is a novel chiral tetradentate phosphine ligand, and the ligand has the advantages of simplicity in synthesis, easiness in modification, good stability and the like. Metal complexes of the ligands show very excellent catalytic activity and extremely high enantioselectivity in asymmetric hydrogenation reaction of ketone, and alpha, beta, beta, beta-tetracarboxylic acid can be efficiently converted into alpha, beta, beta-tetracarboxylic acid, alpha, beta-tetracarboxylic acid and alpha, beta-tetracarboxylic acid. Prochiral ketones such as alpha, beta-unsaturated ketone, simple aryl alkyl ketone, alpha-hydroxy aryl alkyl ketone, alpha-amino aryl alkyl ketone, alpha-chloro aryl alkyl ketone, beta-keto ester and aryl (hetero) aryl ketone are reduced into corresponding chiral alcohols, and the method has important industrial application value.

Description

technical field [0001] The invention belongs to the field of fine chemical industry, relates to a ligand containing a ferrocene structure and its application, in particular to a chiral ferrocene PNNO tetradentate ligand and its application in an asymmetric hydrogenation reaction. Background technique [0002] Asymmetric catalytic hydrogenation has the advantages of good atom economy, high catalytic efficiency, and simple post-treatment, and has become the most important method for the industrial synthesis of chiral compounds. The key to a practical asymmetric hydrogenation technology lies in the metal complex catalyst with high activity and high stereoselectivity, and the ligand is the key and core of the catalyst to obtain excellent performance. Therefore, the development of chiral ligands with novel structures and excellent properties has always been the core content of the research on asymmetric catalytic hydrogenation reactions. [0003] The ferrocene skeleton is a very...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02B01J31/24C07B53/00C07C29/145C07C33/26C07C33/46C07C33/48C07C33/28C07C33/30C07C41/26C07C43/215C07C67/31C07C69/732C07C213/00C07C215/30C07D213/30C07D307/42C07D333/16
CPCY02P20/55
Inventor 吕辉马金铭
Owner WUHAN UNIV
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