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Novel chiral pyridine-containing polydentate nitrogen ligand and palladium complex as well as preparation method and application thereof

A technology of palladium complexes and nitrogen ligands is applied in the field of novel chiral pyridine-containing polydentate nitrogen ligands, which can solve the problems of low enantiomeric selectivity of products, achieve good enantiomeric selectivity, improve efficiency and yield. rate effect

Inactive Publication Date: 2021-08-20
中山大学新华学院
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, palladium complexes for chiral pyridine multi-dentate nitrogen ligands have gradually become the research hotspots of current catalysts. For example, Fiore et al. designed and synthesized pyridine aziridine nitrogen ligands, and after preparing palladium complexes, studied its The catalysis of the asymmetric allylic position substitution reaction, the palladium complex is directly added to the dimethyl malonate / BSA / potassium acetate system for catalysis, but the enantiomeric selectivity of the final product is extremely low, only 10% Left and right (Fiore, K.; Martelli, G.; Monari, M.; Savoia, D. Design and synthesis of enantiopure 1-[1(S)-(2-pyridyl)alkyl]-2(R)-isoropylaziridines, new ligand for asymmetriccatalysis.Tetrahedron:Asymmetry 1999,10,4803-4810)

Method used

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  • Novel chiral pyridine-containing polydentate nitrogen ligand and palladium complex as well as preparation method and application thereof
  • Novel chiral pyridine-containing polydentate nitrogen ligand and palladium complex as well as preparation method and application thereof
  • Novel chiral pyridine-containing polydentate nitrogen ligand and palladium complex as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Example 1 Preparation of novel chiral pyridine-containing multidentate nitrogen ligand Ia

[0034] Dissolve 1mmol of (R)-2-(2-piperidinyl)pyridine in acetonitrile to a concentration of 0.3mol / L, dissolve 0.5mmol of 1,3-dibromopropane in acetonitrile to a concentration of 0.15mol / L, and then add 2mmol Anhydrous potassium carbonate, stirred at 70°C until the thin layer chromatography detected that the raw material point disappeared, then cooled, filtered to remove insoluble matter, and the filtrate was evaporated to dryness under reduced pressure, and the evaporated matter was fully dissolved in dichloromethane, and then hydrated with saturated saline three times Fully wash, retain the washed brine, and back-extract with dichloromethane, collect all the dichloromethane used for back-extraction, dry with anhydrous sodium sulfate, filter to get the filtrate, and after rotary evaporation to dryness, purify with silica gel column chromatography. That is, the novel chiral pyri...

Embodiment 2

[0038] Example 2 Preparation of novel chiral pyridine-containing polydentate nitrogen ligand IIa

[0039] With the method of Example 1, the difference is that (S)-2-(2-piperidinyl)pyridine is used to replace (R)-2-(2-piperidinyl)pyridine, and finally the novel chiral pyridine-containing polyol is obtained. Dental nitrogen ligand IIa, the structure is as follows:

[0040]

[0041] The NMR spectrogram data are as follows:

[0042] 1 H NMR (CDCl 3 ,300MHz):δ8.47(m,2H),7.55(dt,J=7.8,1.8Hz,2H),7.28(d,J=6.9Hz,2H),7.09(m,2H),3.15(dd, J=10.8,2.1Hz,2H),3.03(d,J=11.4Hz,2H),2.01(m,6H),1.64(m,12H),1.34(m,2H). 13 C NMR (CDCl 3 ,600MHz):δ164.47,148.80,136.34,121.67,70.21,53.64,52.61,34.97,25.84,24.62,22.00.ESI-MS(m / z):[M+H] + 365.2.

Embodiment 3

[0043] Example 3 Preparation of novel chiral pyridine-containing polydentate nitrogen ligand Ib

[0044]Same as the scheme in Example 1, the difference is that 1,3-dibromopropane is replaced by 1,6-dibromohexane, and the stirring temperature is 60°C to finally obtain the novel chiral pyridine-containing polydentate nitrogen ligand Ib, The structure is as follows:

[0045]

[0046] The NMR spectrogram data are as follows:

[0047] 1 H NMR (CDCl 3 ,400MHz):δ8.50(d,J=4.0Hz,2H),7.60(dt,J=8.0,4.0Hz,2H),7.36(d,J=8.0Hz,2H),7.11(m,2H) ,3.19(dd,J=12.0Hz,2H),3.13(d,J=12.0Hz,2H),2.22(m,2H),2.03(m,2H),1.89(m,2H),1.78(d, J=12.0Hz, 4H), 1.67(d, J=12.0Hz, 4H), 1.52(m, 2H), 1.34(m, 6H), 0.96(m, 4H). 13 C NMR (CDCl 3 ,600MHz):δ164.82,148.88,136.36,121.73,121.62,70.52,55.76,52.94,35.14,27.22,26.03,25.92,24.72.ESI-MS(m / z):[M+H] + 407.3.

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Abstract

The invention provides a novel chiral pyridine-containing polydentate nitrogen ligand, a palladium complex as well as a preparation method and application thereof. The invention relates to a novel chiral pyridine-containing polydentate nitrogen ligand, the novel chiral pyridine-containing polydentate nitrogen ligand is successfully prepared into a palladium complex, the palladium complex is applied to an asymmetric allylic substitution reaction, the reaction efficiency and yield are greatly improved, the minimum reaction time can reach 2 hours, the yield is as high as 98%, a reaction product can reach better enantiomer selectivity, the ee value is as high as 57%, and a new choice is provided for a novel efficient metal complex catalytic system constructed by carbon-carbon bonds.

Description

technical field [0001] The invention belongs to the technical field of catalyst design. More specifically, it relates to a novel chiral pyridine-containing multidentate nitrogen ligand, a palladium complex, a preparation method and application thereof. Background technique [0002] Chiral pyridine-containing multi-dentate nitrogen ligands, including quadrupyridine derivatives, terpyridine derivatives and pyridine amides, are easy to synthesize, high in stability, have outstanding coordination properties, and can coordinate with a variety of transition metals to form spirochetes, Complexes such as mononuclear metal complexes, and their metal complexes also exhibit significant asymmetric induction when they participate in asymmetric catalytic reactions, including palladium-catalyzed asymmetric allylic substitution reactions, asymmetric cyclopropane reaction and asymmetric hydrosilane addition reaction, etc., especially the palladium-catalyzed asymmetric allylic substitution r...

Claims

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Application Information

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IPC IPC(8): C07D401/14C07F15/00B01J31/22C07C67/343C07C69/618
CPCC07D401/14B01J31/182C07F15/006C07C67/343B01J2531/824B01J2231/4205C07B2200/07C07C69/618
Inventor 成燕琴徐娟娟黎卓熹罗爱勤王有娣
Owner 中山大学新华学院
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