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Planarly chiral ferroceno[1,2-c]-4-quinolinone compound and preparation method thereof

A chiral ferrocene and compound technology, applied in chemical instruments and methods, metallocene, organic chemistry, etc., can solve the problems of narrow application range, environmental pollution, low yield, etc., and achieve mild and easy-to-control reaction conditions. Wide-ranging and easy-to-operate effects

Inactive Publication Date: 2015-01-21
SHANGQIU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are many synthetic methods of quinolinone derivatives, but there are certain problems in many synthetic methods, such as: difficulty in raw material synthesis, serious environmental pollution, low yield, narrow scope of application, etc. The existence of these problems must be Limit the application prospect of quinolinone compounds to a certain extent
In addition, there is still a lack of corresponding research methods for the construction of quinolinone derivatives with stereo configuration [Green Chem.2012,14,3361-3367.]

Method used

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  • Planarly chiral ferroceno[1,2-c]-4-quinolinone compound and preparation method thereof
  • Planarly chiral ferroceno[1,2-c]-4-quinolinone compound and preparation method thereof
  • Planarly chiral ferroceno[1,2-c]-4-quinolinone compound and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Chiral phosphine ligand screening test: Different chiral phosphine ligands L * Catalyzed reactions to obtain different yields and reaction selectivities.

[0026] Under the protection of nitrogen, add N-(2-bromophenyl)-N-methylformamide ferrocene (19.9mg, 0.05mmol) and anhydrous toluene (2.0mL) to the dry Schlenk reaction tube, add in sequence Chiral phosphine ligand L * (0.005mmol), Pd 2 (dba) 3 (2.3mg, 0.0025mmol), pivalic acid (1.5mg, 0.015mmol), cesium carbonate (24.4mg, 0.075mmol), heated to 80 ℃ for 8h. After the reaction, the solvent was removed under reduced pressure, and the target product A was obtained by column chromatography (ethyl acetate / petroleum ether=1 / 10, volume ratio).

[0027]

[0028] Chiral phosphine ligand L * L respectively 1 -L 12 Either of:

[0029] Different Chiral Phosphine Ligands L * Catalyzed reaction, obtained different reaction results, as shown in Table 1 below.

[0030] Table 1 Different chiral phosphine ligands L * The ...

Embodiment 2

[0034] The preparation method of planar chiral ferrocene[1,2-c]-4-quinolinone A with the following structural formula:

[0035]

[0036] Under the protection of nitrogen, add N-(2-bromophenyl)-N-methylformamide ferrocene (19.9mg, 0.05mmol) and anhydrous toluene (2.0mL) to the dry Schlenk reaction tube, add in sequence Chiral phosphine ligand L 12 (2.6mg, 0.005mmol), Pd 2 (dba) 3 (2.3mg, 0.0025mmol), pivalic acid (1.5mg, 0.015mmol), cesium carbonate (24.4mg, 0.075mmol), heated to 80 ℃ for 8h. After the reaction, the solvent was removed under reduced pressure and separated by column chromatography (ethyl acetate / petroleum ether=1 / 10, volume ratio) to obtain 13.3 mg of the target product A (84% yield, 84% ee). Enantiomeric purity was analyzed using Daicel AS-H column: n-hexane / isopropanol=90 / 10, flow rate=1.0 ml / min, retention time: 16.6 minutes (main enantiomer), 13.0 minutes. [α] D 20 =-16 (c=0.04CHCl 3 ,84%ee). 1 H NMR (400MHz, CDCl 3)δ7.70(dd,J=7.6,1.2Hz,1H),7.41-...

Embodiment 3

[0038] The difference between this embodiment and Example 2 is that the catalytic substrate used is N-(2-iodophenyl)-N-methylformamide ferrocene (22.3mg, 0.05mmol), and the product 12.7mg ( 80% yield, 81% ee).

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Abstract

The invention discloses a preparation method of a planarly chiral ferroceno[1,2-c]-4-quinolinone compound, which comprises the following steps: mixing a palladium compound, a chiral phosphine ligand, an acid, an alkali and an organic solvent, adding an N-(2-halogenophenyl)-N-substituted formamide ferrocene compound, heating and stirring to react, concentrating, and purifying to obtain the planarly chiral ferroceno[1,2-c]-4-quinolinone compound. The planarly chiral ferroceno[1,2-c]-4-quinolinone compound is disclosed as general formula I. The planarly chiral ferroceno[1,2-c]-4-quinolinone compound has the advantages of high yield and favorable antipode selectivity, and the antipode selectivity is greater than 90% in most cases. The planarly chiral ferroceno[1,2-c]-4-quinolinone compound can also be used for preparing a chiral ligand, and has very wide application range in metal catalytic asymmetric reaction.

Description

technical field [0001] The invention relates to the technical field of chiral compound synthesis, in particular to a preparation method of a planar chiral ferrocene[1,2-c]-4-quinolinone compound. Background technique [0002] Due to its unique stereostructure and electronic effects, planar chiral ferrocenes have been developed into a class of excellent chiral ligands in asymmetric catalytic reactions, and exhibit high catalytic activity. So far, the common strategy to construct planar chiral ferrocene derivatives with high optical purity is to use various chiral auxiliary groups to induce diastereo-ortho metalation followed by functionalization. In this strategy, it is necessary to pre-introduce central chirality in the ferrocene skeleton; or use stoichiometric external chiral auxiliary agents, lithium reagents and harsh reaction conditions to construct planar chiral ferrocenes. However, there are few reports on the direct construction of planar chiral ferrocene derivatives...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02
CPCC07F17/02
Inventor 刘澜涛周艳丽孟团结王涛许凯李峰赵文献
Owner SHANGQIU NORMAL UNIVERSITY
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