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Pyrido[1,2-a][1,2,4]triazole carbene ligand as well as synthesis method and application thereof

A 2-a, pyridine technology, applied in the field of pyrido[1,2-a][1,2,4]triazolecarbene ligands, can solve the problem that the stability, catalytic activity and selectivity of gold catalyst can no longer be sustained Increase, the electron-richness of the ligand and the steric hindrance cannot be improved indefinitely, so as to achieve the effect of accelerating the addition reaction.

Active Publication Date: 2019-11-22
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, so far, in the design of ligands, most of the classic carbene or some groups are used to modify the carbene to improve its electron-rich and steric hindrance, but the electron-rich and steric hindrance of the ligand cannot be achieved. To achieve unlimited improvement, so the stability, catalytic activity and selectivity of the gold catalyst can no longer continue to improve

Method used

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  • Pyrido[1,2-a][1,2,4]triazole carbene ligand as well as synthesis method and application thereof
  • Pyrido[1,2-a][1,2,4]triazole carbene ligand as well as synthesis method and application thereof
  • Pyrido[1,2-a][1,2,4]triazole carbene ligand as well as synthesis method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Pyrido[1,2-a][1,2,4]triazole carbene ligand, which is a compound described in formula (1):

[0039]

[0040] The compound is prepared as follows:

[0041] Step 1: To a solution of 3-iodobenzoic acid (10 mmol) in anhydrous dichloromethane (50 mL) was added oxalyl chloride (25 mmol) and three drops of N,N-dimethylformamide, and the mixture was stirred at room temperature 2-4 hours. The reaction mixture was evaporated under reduced pressure and dried under vacuum to give 3-iodobenzoyl chloride which was redissolved in 50 mL of anhydrous dichloromethane and cooled in an ice bath before addition of tetrahydropyrrole (15 mmol) and triethylamine (20mmol) in dichloromethane solution (10mL), reacted at room temperature under an inert atmosphere for 1 hour, then the solution was treated with 50mL water and 100mL dichloromethane, the organic phase was separated, dried, the solvent was evaporated, and then separated by column chromatography, Using a mixed solvent of petroleum ...

Embodiment 2

[0059] Synthesis of pyrido[1,2-a][1,2,4]triazole carbene-gold complexes:

[0060]

[0061] Protect from light, under an inert atmosphere, add pyrido[1,2-a][1,2,4]triazolecarbene ligand V (1mmol) into the reaction tube, dry tetrahydrofuran (2mL), add bistrisulfate at -78°C Lithium methylsilylamide (1.1mmol), after stirring for 15min, add dimethyl sulfide gold chloride, stir and react for 16 hours, evaporate the solvent, and then separate by column chromatography, with methanol at a volume ratio of 1:100 The mixed solvent of dichloromethane is the eluent, and the eluate containing the target product is collected and spin-dried to obtain pyrido[1,2-a][1,2,4]triazolecarbene-gold complex VI, white Solid, 85% yield.

[0062]

Embodiment 3

[0064] Pyrido[1,2-a][1,2,4]triazole carbene-gold complex catalyzed the synthesis of 1,4-benzodiazepine from phenylacetylene

[0065]

[0066] At room temperature, add pyrido[1,2-a][1,2,4]triazolecarbene-gold complex (0.01mmol), AgNTf 2 (0.02 mmol), stirred for 15 minutes. Then add 1,2-phenylenediamine (0.2mmol), phenylacetylene (0.5mmol), and then stir at room temperature for 6 hours and then separate by column chromatography. The solvent is the eluent, and the eluate containing the target product is collected and spin-dried to obtain the 1,4-benzodiazepine product.

[0067]

[0068] Yellow solid, 80% yield. 1 H NMR (500MHz, CDCl3) δ7.66–7.58(m,4H),7.38–7.23(m,6H),7.20(t,J=7.3Hz,1H),7.09(m,J=11.9,7.4,1.5 Hz,2H),6.87(dd,J=7.5,1.3Hz,1H),3.56(s,1H),3.17(d,J=13.2Hz,1H),3.00(d,J=13.2Hz,1H), 1.78(s,3H).

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Abstract

The invention provides a pyrido[1,2-a][1,2,4]triazole carbene ligand as well as a synthesis method and application thereof. A pyrido[1,2-a][1,2,4]triazole carbene-gold complex formed from the pyrido[1,2-a] [1,2,4]triazole carbene ligand shown as a formula V and gold can be applied to alkyne catalytic addition reaction, has Lewis acid / alkali double activation centers, and can depend on the 'synergistic activation effect' of the double activation centers, so that the catalytic effect which cannot be achieved or cannot be achieved by a conventional ligand is achieved, and the addition reaction ofa nucleophilic reagent to multiple bonds can be greatly accelerated.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to a pyrido[1,2-a][1,2,4]triazole carbene ligand, a synthesis method thereof, a gold complex and an application thereof. Background technique [0002] The successful application of gold in the field of catalysis is one of the important milestones in the development of chemical research in the past ten years. In the study of homogeneous gold, how to effectively improve the stability, catalytic activity and selectivity of gold catalysts is always the core content of gold catalyst design. Among them, the nitrogen-heterocyclic carbene ligands with electron-rich and large steric hindrance properties are widely used in the ligand design of gold catalysts, because such electron-rich and large steric hindrance ligands will affect them with their unique electronic effects and steric effects. The electronic state and three-dimensional environment of the central metal gold will profoundly a...

Claims

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Application Information

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IPC IPC(8): C07D471/04C07F1/12B01J31/22C07D243/12
CPCB01J31/2273B01J2231/324B01J2531/18C07D243/12C07D471/04C07F1/12
Inventor 刘运奎郑康河周丙伟
Owner ZHEJIANG UNIV OF TECH
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