Dipyridine ligands with axial chirality and synthetic method thereof

A synthetic method and bipyridine technology, applied in the direction of organic chemistry, etc., can solve the problems of seldom reported applications and less development of pyridine ligands, and achieve the effects of high yield, few reaction steps, and high yield

Active Publication Date: 2016-06-22
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] From the above examples, we can see that the development of axial chiral bipyridyl ligands that conduct and contro

Method used

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  • Dipyridine ligands with axial chirality and synthetic method thereof
  • Dipyridine ligands with axial chirality and synthetic method thereof
  • Dipyridine ligands with axial chirality and synthetic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Embodiment 1: the synthesis of bipyridine ligand 4

[0042]

[0043] Add diol 1 (2.080g, 20mmol), pyridine 2 (9.72g, 44mmol), and triphenylphosphine (12.6g, 48mmol) into a 250mL reaction flask under nitrogen protection, and add 80mL tetrahydrofuran at 0°C and stir to dissolve. DIAD (9.70 g, 48 mmol) was dissolved in 20 mL of tetrahydrofuran solution dropwise from the constant pressure dropping funnel. After the dropwise addition, the system was an orange-red transparent solution. After 28 hours of reaction, only a small amount of raw materials remained, and the reaction was stopped.

[0044] First spin dry THF, add 20mL dichloromethane to dissolve, add a large amount of petroleum ether, until a large amount of solids precipitate (mostly the reduction product of triphenoxyphosphine and DIAD. If it cannot be precipitated, scrape the bottle wall repeatedly with a small spoon), pump Filtrate (wash the solid with petroleum ether several times during suction filtration, c...

Embodiment 2

[0046] Embodiment 2: the synthesis of bipyridine ligand 8

[0047]

[0048] Add pyridine 5 (6.458g, 60mmol) to tetrahydrofuran / water (50 / 50mL) mixed solution, stir to dissolve and then add iodine (16.8g, 66mmol) and sodium bicarbonate (5.281g, 66mmol) to the reaction flask, at room temperature After 3 days of reaction, the reaction solution was purple-black, and solids were precipitated. Add 10% sodium thiosulfate solution until the purple-black color disappeared, and a large amount of white solids precipitated. 8.19 g of off-white solids were obtained by suction filtration, which was verified as product 6 by NMR.

[0049] Add diol (2.080g, 20mmol), pyridine 6 (10.3g, 44mmol), and triphenylphosphine (12.6g, 48mmol) into a 250mL reaction flask under nitrogen protection, and add 80mL tetrahydrofuran at 0°C and stir to dissolve. DIAD (9.70 g, 48 mmol) was dissolved in 20 mL of tetrahydrofuran solution dropwise from the constant pressure dropping funnel. After the dropwise addi...

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Abstract

The invention relates to dipyridine ligands with axial chirality. A synthetic method adopts 3-hydroxy-2-halogen pyridine as an initial raw material, and includes loading a chiral skeleton with the pyridine through a Mitsunobu reaction with a chiral diol, and achieving pyridine coupling through an Ullman reaction catalyzed by nickel (0) or copper (0) to obtain the dipyridine ligands induced by the chiral diol. The method is simple and convenient in operation and high in yield. The synthetic method is more practical when being compared with traditional methods.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a class of bipyridine ligands with axial chirality and a synthesis method thereof. Background technique [0002] Chiral bipyridyl ligands have been widely concerned by scientific researchers since they were first synthesized in 1984, and thus have been rapidly developed and applied. Chiral bipyridyl ligands can coordinate with a variety of metals to catalyze a series of asymmetric reactions, and gradually develop into an important class of ligands in asymmetric catalytic reactions, especially in reactions catalyzed by transition metals. Therefore, the design and synthesis of novel chiral bipyridyl ligands is still an important part of asymmetric catalysis research [1] . (Document 1: Thummel, R.P; Chelucci, G. Chem. Rev. 2002, 102, 3129.) [0003] Compared with central chiral and planar bipyridyl ligands, there are relatively few studies on axial chiral bipyridyl li...

Claims

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Application Information

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IPC IPC(8): C07D491/147
Inventor 周永贵高翔吴波
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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