Application of metallide/palladium compound catalytic reduction system in reaction of removing allyl groups and deuteration reaction

A palladium compound, metallization technology, applied in the direction of organic compound/hydride/coordination complex catalyst, cyanide reaction preparation, preparation of organic compounds, etc., to achieve the effect of wide substrate range, small molecular weight and easy availability

Active Publication Date: 2018-06-29
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although it has been used for more than 100 years, sodium hydrid...

Method used

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  • Application of metallide/palladium compound catalytic reduction system in reaction of removing allyl groups and deuteration reaction
  • Application of metallide/palladium compound catalytic reduction system in reaction of removing allyl groups and deuteration reaction
  • Application of metallide/palladium compound catalytic reduction system in reaction of removing allyl groups and deuteration reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031]

[0032] Under nitrogen protection, palladium acetate (0.018 mmol, 6 mol%) and sodium hydride (60% in oil, 0.51 mmol, 1.7 equiv) were suspended in DMA (1.0 mL), stirred at 25°C for 5 minutes, and compound 1 (0.3 mmol) was added solution in DMA (0.5mL), then reacted at 25°C for 4 hours, added ice water to stop the reaction, adjusted the pH value to 3.5 with dilute hydrochloric acid, extracted with ethyl acetate, combined the extracts, dried with sodium sulfate, and rotary evaporated Drying and purification by column chromatography gave product 2 with a yield of 99%. 1 H NMR (400 MHz, DMSO-d 6 ): δ 10.10 (br, 1H), 8.13 (d, J = 7.9 Hz, 1H), 7.80 (d, J =7.7 Hz, 1H), 7.51-7.37 (m, 2H), 7.31 (q, J = 8.0 Hz, 2H), 6.87 (d, J = 6.8Hz, 1H); 13 C NMR (151 MHz, DMSO-d 6 ): δ 153.12, 134.38, 127.34, 126.39, 126.04, 124.53, 124.50, 121.94, 118.29, 108.00. LR-MS (ESI): m / z 145.1 [M+H] + .

Embodiment 2

[0034]

[0035]Under nitrogen protection, palladium chloride (0.006 mmol, 2 mol%) and lithium hydride (0.9 mmol, 3 equiv) were suspended in THF (1.0 mL), stirred at 25°C for 5 minutes, compound 1 (0.3 mmol) was added in THF (0.5 mL), then reacted at 80°C for 1 hour, added ice water to stop the reaction, adjusted the pH value to 3.5 with dilute hydrochloric acid, extracted with ethyl acetate, combined the extracts, dried with sodium sulfate, evaporated to dryness, and column layer Purified by analysis to obtain product 2 with a yield of 92%.

Embodiment 3

[0037]

[0038] Under nitrogen protection, Pd(MeCN) 2 Cl 2 (0.003 mmol, 1 mol%) and potassium hydride (0.3 mmol, 1 equiv) were suspended in DMF (1.0 mL), stirred at 25°C for 5 minutes, a solution of compound 1 (0.3 mmol) in DMF (0.5 mL) was added, and then in React at -50°C for 36 hours, add ice water to stop the reaction, adjust the pH value to 3.5 with dilute hydrochloric acid, extract with ethyl acetate, combine the extracts, dry with sodium sulfate, evaporate to dryness by rotary evaporation, and purify by column chromatography to obtain the product 2 , yield 84%.

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PUM

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Abstract

The invention discloses application of a metallide/palladium compound catalytic reduction system in reaction of removing allyl groups of a compound containing the allyl groups and deuteration reaction. The reaction comprises the following steps: under protection of nitrogen gas, suspending a palladium compound and a metallide in a solvent, stirring for 5 minutes, adding the compound containing theallyl groups, reacting for 0.5-36 hours at the temperature of minus 50-120 DEG C, adding ice water to stop reaction, regulating a pH value to 3.5 by using diluted hydrochloric acid, and carrying outsolvent extraction, drying by steaming and column-chromatography purification on reaction liquid to finish the reaction.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to the application of a metal hydride (deuterium) compound / palladium compound catalytic reduction system in deallylation and deuteration reactions. Background technique [0002] Sodium hydride is a strong base that is often used in laboratories and industries, and is usually used for hydrogen extraction of substrates to form corresponding sodium salts. Although it has been used for more than 100 years, sodium hydride is rarely used as a reducing agent, and there are few related reports. Until recently, several research groups reported new uses of sodium hydride as a reducing agent. For example, sodium hydride is used as a reducing agent to reduce amides to aldehydes, and bromobenzene debromination, etc., but a large excess of sodium hydride is required here, and at least 2 equivalents of sodium iodide are required as accelerators; another example is at 1,10 -...

Claims

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Application Information

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IPC IPC(8): C07C37/055C07C39/14C07C39/21C07C41/26C07C43/23C07C253/30C07C255/53C07C45/64C07C47/565C07C49/825C07C201/12C07C205/22C07D239/88C07D209/08C07C227/02C07C229/60C07C51/09C07C63/70C07C65/21C07C63/04C07D207/16C07C41/18C07C43/215
CPCC07C37/055B01J31/121B01J27/13C07C39/14
Inventor 张士磊刘晔毛玉健桂晶晶孙婉婉王柳迪
Owner SUZHOU UNIV
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