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A chiral tridentate pnn ligand and its application in asymmetric hydrogenation reactions

An asymmetric and chiral technology that can be used in asymmetric synthesis, preparation of organic compounds, organic compound/hydride/coordination complex catalysts, etc., and can solve problems such as complex synthesis routes

Active Publication Date: 2017-12-08
SHENZHEN CATALYS SCI & TECH CO LTD +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But in comparison, the synthetic route of SpiroPAP ligand is more complicated

Method used

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  • A chiral tridentate pnn ligand and its application in asymmetric hydrogenation reactions
  • A chiral tridentate pnn ligand and its application in asymmetric hydrogenation reactions
  • A chiral tridentate pnn ligand and its application in asymmetric hydrogenation reactions

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] Example 1 Synthesis of L21f-(S)-(R)-amphox

[0059]

[0060] N 2 A hexane solution of n-butyllithium (12.4mL, 1.4M) under protection was added dropwise to (3.6g, 14mmol) of (S)-1 in 20mL of anhydrous diethyl ether solution, keeping the temperature at 0°C and controlling Dropping time was 20 minutes. After the dropwise addition, the reaction solution was stirred at room temperature for 1.5 h, and then a solution of diphenylphosphine chloride (6.2 g, 28 mmol) in 10 mL of diethyl ether was slowly added dropwise. After the dropwise addition was completed, it was refluxed for 4h. Cool the reaction solution to room temperature, put it in an ice-water bath, slowly add a saturated aqueous solution of sodium bicarbonate dropwise, and extract the orange-yellow product with ether, combine the organic phases, wash with water, dry over anhydrous sodium sulfate, and dry in vacuo to obtain an orange oil liquid. After column purification and recrystallization from ethanol, 2.97 ...

Embodiment 2

[0072] Synthesis of Example 2 L25(R)-amphox

[0073]

[0074] N 2 CH under protection to 2-chloroethylamine hydrochloride (1 g, 8.62 mmol) 2 Cl 2 (20mL) solution was added Boc 2 O (2.07 g, 9.48 mmol) and triethylamine (1.56 mL, 11.2 mmol). After the reaction solution was stirred at room temperature for 24 h, TLC monitored the completion of the reaction and added water to separate the organic phase, and the water phase was separated with CH 2 Cl 2 Extracted three times with anhydrous Na 2 SO 4 After drying and filtration, the solvent was removed under reduced pressure. The target product 2 was purified by column chromatography as a yellow oil with a yield of 97%.

[0075]

[0076] 0°C, N 2 Ph 2 PH (18.6g, 100mmol) was slowly added dropwise into the anhydrous THF solution of t-BuOK (13.5g, 120mmol), after the dropwise addition was completed, it was raised to room temperature and stirred for 40min, then the raw material 2 was slowly added to the reaction solution ...

Embodiment 3

[0081] The synthesis of embodiment 3 (R)-amphox catalyst

[0082]

[0083] RuHCl(CO)(PPh 3 ) 3 (0.95g, 1mmol) and the ligand L25(R)-amphox (0.42g, 1.05mmol) were put into 7ml of anhydrous and oxygen-free 1,4-dioxane solvent, heated to reflux for 3h and then cooled to room temperature. Diethyl ether was added to the system and the temperature was lowered to -15°C to obtain crystals and filtered. The solid was washed twice with ether and then dried in vacuo to obtain a yellow solid with a yield of 88%, which indicated that the catalyst could be used for catalytic reactions without purification.

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Abstract

The invention discloses a class of chiral tridentate nitrogen phosphine ligand and its application in asymmetric hydrogenation and similar reactions. The tridentate nitrogen phosphine ligand disclosed in the present invention is the first chiral oxazoline-containing tridentate nitrogen phosphine ligand, and has been successfully applied to the hydrogenation reaction of ketones and imide salts and similar reactions with high efficiency and high selectivity . Compared with other ligands, the synthetic route is simple, the yield is high, and it is more environmentally friendly. In addition, the metal complexes of this type of ligand not only show better selectivity in asymmetric hydrogenation reactions, but also show higher conversion numbers . The iridium complex of the chiral tridentate nitrogen phosphine ligand of the present invention has successfully asymmetrically reduced β-ketone lipids to β-alcohol lipids (raw materials for the synthesis of molecular drugs duloxetine and atomoxetine), and α ‑Hydroxyacetophenone asymmetrically hydrogenates α‑hydroxyphenylethanol, and asymmetrically hydrogenates acetophenone to phenylethyl alcohol, which is of great significance for the production of the pharmaceutical industry.

Description

technical field [0001] The invention relates to a chiral tridentate nitrogen phosphine ligand and its application in asymmetric hydrogenation reaction, which belongs to the field of fine chemical industry. Background technique [0002] Chiral compounds are widely used in pesticides, medicine, food, materials, fine chemicals and other fields, and are of great significance. With the improvement of living standards, people's demand for medicine and fine chemical products has greatly increased. In 2010, the global drug production value reached 880 billion US dollars, and generic drugs reached 103 billion US dollars. As the third largest pharmaceutical market in the world, China contains huge market opportunities. Therefore, scientists need to explore more efficient and environmentally friendly methods to design and selectively synthesize monochiral molecules. Asymmetric catalytic reaction is the most economical and efficient way to synthesize chiral compounds, and a large amo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/653B01J31/24C07F17/02C07B53/00C07D333/20C07D413/06C07D453/02C07D401/12C07D215/18C07C217/48C07C213/02C07D223/22C07D213/75C07D205/08C07F9/6558C07D401/14C07C67/31C07C69/732C07C69/734C07C29/143C07C33/26C07C33/46C07C33/20C07D333/16
Inventor 张绪穆
Owner SHENZHEN CATALYS SCI & TECH CO LTD
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