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Method for catalyzing decarboxylation of active carboxylic ester to introduce nitrogen heterocycle through photo-induced non-metal

A carboxylate, light-induced technology, applied in organic chemistry and other directions, can solve the problems of high price of iridium, increased production cost, easy residue, etc., and achieve the effect of large synthetic value prospect, substrate scope and good functional group compatibility.

Active Publication Date: 2019-01-04
UNIV OF SCI & TECH OF CHINA
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In order to solve the problem that the use of noble metal catalysts such as iridium in the prior art not only increases the production cost due to the high price of iridium but also tends to remain in the resulting product, the present invention provides a photoinitiated non-metallic catalytic active carboxylate decarboxylation introduced The nitrogen heterocycle method does not require the addition of metal catalysts, and the reaction conditions are mild, and it has good compatibility with functional groups

Method used

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  • Method for catalyzing decarboxylation of active carboxylic ester to introduce nitrogen heterocycle through photo-induced non-metal
  • Method for catalyzing decarboxylation of active carboxylic ester to introduce nitrogen heterocycle through photo-induced non-metal
  • Method for catalyzing decarboxylation of active carboxylic ester to introduce nitrogen heterocycle through photo-induced non-metal

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Embodiment 1, preparation 2-cyclohexyl-4-methylquinoline

[0056] Reaction formula:

[0057] (where Cy represents cyclohexyl)

[0058] The specific method is as follows:

[0059] Add NaI (0.02mmol (that is, 10mol% of the nitrogen-containing heterocyclic compound 1a. ), 3mg), PPh 3 (0.04mmol (that is, 20mol% of the nitrogen-containing heterocyclic compound 1a. The same below), 10.5mg) and 1,3-dioxoisoindolin-2-ylcyclohexanecarboxylate (2a, 0.3 mmol, 81.9 mg). The air in the tube was completely replaced with argon three times, and then 2 mL of acetone, trifluoroacetic acid (0.2 mmol, 22.8 mg), and 4-methylquinoline (1a, 0.2 mmol, 28.6 mg) were added under an argon atmosphere. The reaction system was continuously stirred for 15 hours at room temperature under the irradiation of a blue LED lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction is complete, use H 2 The reaction was quenched with O, and the reaction solution was extra...

Embodiment 2

[0062] Embodiment 2, preparation 4-methyl-2-(pent-2-yl) quinoline

[0063] Reaction formula:

[0064]

[0065] The specific method is as follows:

[0066] Add NaI (10mol%, 3 mg) and PPh into a 10mL Schlenk reaction tube (Beijing Shinwell Glass Instrument Co., Ltd., F891410 reaction tube, capacity 10mL, ground 14 / 20) 3 (20mol%, 10.5mg) and 1,3-dioxoisoindolin-2-yl 2-methylpentanoate (0.3mmol, 78.3mg). The air in the tube was completely replaced with argon three times, and then 2 mL of acetonitrile, trifluoroacetic acid (0.2 mmol, 22.8 mg), and 4-methylquinoline (0.2 mmol, 28.6 mg) were added under an argon atmosphere. The reaction system was continuously stirred for 17 hours at room temperature under the irradiation of a blue LED lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction is complete, use H 2 The reaction was quenched with O, and the reaction solution was extracted with ethyl acetate (3*10 mL), and the combined organic phase w...

Embodiment 3

[0070] Example 3, preparation of 2-(2,3-dihydrobenzo[b][1,4]dioxin-2-yl)-4-methylquinoline

[0071] Reaction formula:

[0072]

[0073] The specific method is as follows:

[0074] Add NaI (20mol%, 6 mg), PPh into a 10mL Schlenk reaction tube (Beijing Xinweier Glass Instrument Co., Ltd., F891410 reaction tube, capacity 10mL, ground 14 / 20) 3(20mol%, 10.5mg) and 1,3-dioxoisoindolin-2-yl 2,3-dihydrobenzo[b][1,4]dioxin-2-carboxylate (0.3 mmol, 97.5mg). The air in the tube was completely replaced with argon three times, and then 2 mL of N,N-dimethylacetamide, trifluoroacetic acid (0.2 mmol, 22.8 mg), 4-methylquinoline (0.2 mmol, 28.6 mg) were added under an argon atmosphere. ). The reaction system was continuously stirred for 17 hours at room temperature under the irradiation of a blue LED lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction is complete, use H 2 The reaction was quenched with O, and the reaction solution was extracted with...

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Abstract

The invention provides a method for catalyzing decarboxylation of active carboxylic ester to introduce a nitrogen heterocycle through a photo-induced non-metal. According to the method, the decarboxylation of the active carboxylic ester is realized through light in the presence of a simple iodised salt, a phosphine ligand and an organic solvent, and the nitrogen heterocycle is introduced by a minisci reaction with a nitrogen-containing heterocyclic compound. The method provided by the invention utilizes photocatalysis to achieve high-efficiency catalytic conversion at room temperature, and ismild in reaction conditions and simple to operate; compared with previously reported conventional methods, the method avoids the use of precious metal catalysts and meets the requirements for developing green and environmentally-friendly chemistry, and substrates are wide in range and good in functional group compatibility; and the method can be successfully applied to gram-grade scale-up experiments, the conversion rate of reactions is high, and industrial synthesis value prospects can be achieved.

Description

technical field [0001] The invention relates to the field of compound synthesis, in particular to a method for light-induced decarboxylation of non-metallic catalytically active carboxylate to introduce nitrogen heterocycle. Background technique [0002] Aromatic heterocyclic compounds are extremely important structural units in the field of medicinal chemistry, and functionalization of aromatic heterocyclic rings through selective catalysis is one of the important means to discover new drugs. The main method to achieve the functionalization of aromatic heterocycles is the known Minisci reaction, as has been reported with Photoredox / Acid Co-Catalysis EnablingDecarboxylative Coupling of Amino Acid and Peptide Redox-Active Esters withN- Heteroarenes, Wan-Min Cheng, Rui Shang, and Yao Fu, ACS Catal.2017, 7, 907-911; Photoredox-Catalysed Decarboxylative Alkylation of N- Heteroarenes with N-(Acyloxy)phthalimides, Wan-Min Cheng, Rui Shang, Ming-Chen Fu, and Yao Fu, Chem. Eur. J...

Claims

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Application Information

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IPC IPC(8): C07D215/06C07D405/04C07D215/14C07D401/04C07D215/12C07D401/06C07D217/02C07D221/12C07D215/233C07D413/04C07D213/80
CPCC07D213/80C07D215/06C07D215/12C07D215/14C07D215/233C07D217/02C07D221/12C07D401/04C07D401/06C07D405/04C07D413/04
Inventor 傅尧王佳鑫尚睿吴雅楠付明臣
Owner UNIV OF SCI & TECH OF CHINA
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