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Azacyclic carbene carboxylate bidentate ligand, bidentate ruthenium complex and preparation method and application of catalyzing carboxylic acid-alkyne addition

A technology for carbene carboxylic acid and ruthenium complexes, which is applied in the field of carbene ruthenium complex synthesis, can solve the problems of poor stability of metal ruthenium catalysts, harsh reaction conditions, short service life, etc., and achieves good catalytic activity, high catalytic yield, and durability. saved effect

Active Publication Date: 2021-07-27
CAPITAL NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Moreover, the only metal ruthenium system that catalyzes the intramolecular carboxylic acid-alkyne addition reaction is mostly carried out at a relatively high temperature (>100°C), and the reaction conditions are harsh, which is not conducive to operation. At the same time, the prepared metal ruthenium catalyst Poor stability and short service life

Method used

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  • Azacyclic carbene carboxylate bidentate ligand, bidentate ruthenium complex and preparation method and application of catalyzing carboxylic acid-alkyne addition
  • Azacyclic carbene carboxylate bidentate ligand, bidentate ruthenium complex and preparation method and application of catalyzing carboxylic acid-alkyne addition
  • Azacyclic carbene carboxylate bidentate ligand, bidentate ruthenium complex and preparation method and application of catalyzing carboxylic acid-alkyne addition

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Embodiment 1: the synthesis of Ru-L1, Ru-L2, synthetic route is as figure 1 shown.

[0038] 1. Synthesis of nitrogen heterocyclic carbene carboxylate bidentate ligand L1: 5 mmol of 1-methylimidazole and 5.5 mmol of methyl chloroacetate were reacted in 7 mL of acetonitrile at 90° C. for 24 hours, then the solvent was drained, and diethyl ether was used to Get washed.

[0039] Synthesis of nitrogen heterocyclic carbene carboxylate bidentate ligand L2: 5 mmol of 1-phenylimidazole and 5.5 mmol of methyl chloroacetate in 7 mL of acetonitrile, reacted at 90 ° C for 24 hours, dried the solvent, and washed with ether to obtain .

[0040]

[0041] 2. Synthesis of Ru-L1 and Ru-L2

[0042]

[0043] Mix the azacyclic carbene carboxylate bidentate ligand L1 / azacyclic carbene carboxylic acid bidentate ligand L2 (0.5 mmol) and silver oxide (0.66 mmol) in 10 mL of dichloromethane, and react in the dark at room temperature for 24 Hours, the filtered silver carbene intermediate...

Embodiment 2

[0046] Embodiment 2: the synthesis of Ru-L3, Ru-L4, synthetic route is as figure 1 shown.

[0047] 1. Synthesis of nitrogen heterocyclic carbene carboxylate bidentate ligand L3: 5 mmol of 1-methyl-2-phenylimidazole and 5.5 mmol of methyl chloroacetate in 10 mL of acetonitrile, reacted at 90 ° C for 24 hours The solvent was drained and washed with ether.

[0048] Synthesis of nitrogen heterocyclic carbene carboxylate bidentate ligand L4: 5mmol 1,2-diphenylimidazole and 5.5mmol methyl chloroacetate were reacted in 10mL acetonitrile at 90°C for 24 hours, then the solvent was drained, and the obtained by washing with ether.

[0049]

[0050] 2. Synthesis of Ru-L3 and Ru-L4

[0051]

[0052] Mix the azacyclic carbene carboxylate bidentate ligand L3 / azacyclic carbene carboxylic acid bidentate ligand L4 (0.5mmol) and silver oxide (0.66mmol) in 10mL of dichloromethane, and react in the dark at room temperature for 24 Hours, the filtered silver carbene intermediate solution w...

Embodiment 3- Embodiment 11

[0056] Embodiment 3-Example 11: Intramolecular addition reaction of alkynoic acid in deuterated chloroform, synthetic route such as figure 2 shown.

[0057] With 0.2mmol alkynoic acid as the reaction substrate, dissolve in 1mL CDCl 3 In, add the nitrogen heterocyclic carbene carboxylate bidentate ruthenium complex of different substance amounts (catalyst amount is the percentage of the amount of alkynoic acid substance), the sealing reaction temperature is 60 ℃, examines reaction time respectively 4h, 2 / 3h and 24h The reaction situation, after the reaction is completed, it is directly transferred to the NMR tube, and the NMR spectrum of the crude product is tested, and the NMR yield is calculated accordingly.

[0058] The catalyzer of embodiment 3-embodiment 11, catalyst addition, reaction time namely productive rate are as shown in table 1.

[0059] Table 1 shows the catalytic condition screening and substrate expansion of carboxylic acid-alkyne intramolecular addition rea...

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Abstract

The invention discloses a nitrogen heterocyclic carbene carboxylate bidentate ligand and a bidentate ruthenium complex, a preparation method and its application in catalyzing the addition of carboxylic acid-alkynes. The compound is synthesized by using imidazole and its derivatives and methyl chloroacetate as raw materials. Bidentate ligands containing imidazolium groups, nitrogen heterocyclic carbene chelate ligands are transferred metallized to obtain nitrogen heterocyclic carbene carboxylate bidentate ruthenium complexes; nitrogen heterocyclic carbene carboxylate bidentate ruthenium complexes are used as catalysts , to catalyze intramolecular or intermolecular carboxylic acid-alkyne addition reactions. The complex provided by the invention has good catalytic activity for carboxylic acid-alkyne addition reaction, especially intramolecular addition reaction, milder temperature and higher catalytic yield. For the first time, a mesoionic nitrogen-heterocyclic carbene-ruthenium complex was used to catalyze the addition of carboxylic acid-alkynes.

Description

technical field [0001] The invention relates to the technical field of synthesis of carbene ruthenium complexes. Specifically, it relates to nitrogen heterocyclic carbene carboxylate bidentate ligands and bidentate ruthenium complexes, preparation methods and applications for catalyzing carboxylic acid-alkyne addition. Background technique [0002] Catalytic intramolecular and intermolecular carboxylic acid-alkyne addition is a kind of method to construct enoate (Hintermann, L., Top. Organomet. Chem., 2010, 31, 123-155; Bruneau, C., Top. Organomet .Chem.,2013,43,203-230; Abbiati,G.; Beccalli,E.M.,Rossi,E.,Top.Organomet.Chem.,2013,43,231-290;Javier F.,Victorio C.,Catalysts,2017,7,328 .). Catalyzing intramolecular and intermolecular additions to obtain unsaturated (lactone) products, which are common structural units in natural products and bioactive molecules, and are also valuable synthetic intermediates (Rao, Y.S., Chem. Rev., 1976, 76, 625-694; Laduwahetty, T., Contemp....

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D233/06C07F15/00B01J31/22C07D307/88C07C67/04C07C69/78
CPCB01J31/2278B01J2231/32B01J2531/0225B01J2531/0233B01J2531/821C07C67/04C07D233/06C07D307/88C07F15/0046C07C69/78
Inventor 郭帅胡艳艳崔柳
Owner CAPITAL NORMAL UNIVERSITY
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