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Method for synthesizing chiral indoline through palladium catalyzed asymmetric hydrogenation of indole generated in situ

An in-situ generation and chemical synthesis technology, which is applied in the field of indole synthesis of chiral indolines, can solve the problems of difficulty and instability in indole synthesis, and achieves the effects of simple and practical reaction operation, convenient preparation and mild reaction conditions.

Active Publication Date: 2020-02-14
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above strategies also face some limitations, such as the difficulty in synthesis and the relative instability of indole

Method used

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  • Method for synthesizing chiral indoline through palladium catalyzed asymmetric hydrogenation of indole generated in situ
  • Method for synthesizing chiral indoline through palladium catalyzed asymmetric hydrogenation of indole generated in situ
  • Method for synthesizing chiral indoline through palladium catalyzed asymmetric hydrogenation of indole generated in situ

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-16

[0025] Optimization of hydrogenation reaction conditions

[0026] Under nitrogen atmosphere, drop into palladium precursor (1mol%-5mol% of substrate consumption) and chiral bisphosphine ligand (1.1mol%-5.5mol% of substrate consumption) in reaction bottle, add acetone (1.0-2.0 mL), stirred at room temperature for 1 h, and then removed acetone under reduced pressure, then brought the catalyst into the glove box, dissolved the catalyst with the organic solvent used for hydrogenation, and transferred it to a mixture containing additives (1.0-2.0 equiv. 0.2mmol reaction bottle, then put the reaction bottle into the reaction kettle, pass in hydrogen (10psi-1000psi), react at 0-80°C for 12-48 hours; release hydrogen, remove the solvent under reduced pressure, add carbonic acid Aqueous sodium hydrogen solution, extracted with DCM, combined the organic layers, removed the solvent under reduced pressure, and separated by column chromatography to obtain a pure product. 16 different exam...

Embodiment 17-30

[0033] Synthesis of Chiral Indoline 2 by Palladium-Catalyzed Asymmetric Hydrogenation of Indole Generated in Situ

[0034]Under nitrogen atmosphere, drop into palladium precursor (1mol%-5mol% of substrate consumption) and chiral bisphosphine ligand (1.1mol%-5.5mol% of substrate consumption) in reaction bottle, add acetone (1.0-2.0 mL), stirred at room temperature for 1h, and then removed acetone under reduced pressure, then brought the catalyst into the glove box, dissolved the catalyst with the solvent used for hydrogenation, and transferred it to a mixture containing additives (1.0-2.0 equiv. 0.25mmol reaction bottle, then put the reaction bottle into the reaction kettle, pass in hydrogen gas (10psi-1000psi), react at 0-80°C for 12-48 hours; release hydrogen gas, remove the solvent under reduced pressure, add hydrogen carbonate Sodium aqueous solution, DCM extraction, merging of organic layers, decompression to remove solvent, column chromatography separation to obtain pure ...

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Abstract

The invention discloses a method for synthesizing chiral indoline through palladium-catalyzed asymmetric hydrogenation of indole generated in situ. The method is characterized in that an indole compound generated in situ is subjected to asymmetric hydrogenation by using 1-5 mol% of a palladium catalyst and adding 1-2.0 equev acid to obtain a corresponding chiral indoline compound, wherein the enantiomeric excess can reach 96% at most. According to the invention, the method is simple and convenient to operate, practical, easy to implement, high in yield, environmentally friendly, available in catalyst business and mild in reaction condition, and has potential practical application value.

Description

technical field [0001] The invention relates to a method for synthesizing chiral indoline by using palladium homogeneous system to highly enantioselectively catalyze the hydrogenation of indole generated in situ, and belongs to the field of asymmetric catalytic synthesis. Background technique [0002] Chiral indoline compounds widely exist in natural products and biologically active molecules, possess a broad spectrum of physiological activities, and can be used as pharmaceuticals, insecticides, herbicides, etc. (Reference 1: (a) I.W. Southon and J.Buckingham, Dictionary of Alkaloids, Chapman and Hall, New York, 1989; (b) D. Zhang, H. Song and Y. Qin, Acc. Chem. Res., 2011 ,44, 447.For some examples,see:(c)W.-G.Kim,J.-P.Kim,H.Koshino,K.Shin-Ya,H.Setoand I.-D.Yoo,Tetrahedron, 1997, 53, 4309; (d) R.M. Jones, S. Han and J.V. Moody, Patent Appl. WO 2009151626, 2009). Based on this, the asymmetric synthesis of chiral indoline and its derivatives has attracted extensive attentio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/08C07D209/12B01J31/24
CPCB01J31/2495B01J2531/0261B01J2531/824C07B2200/07C07D209/08C07D209/12
Inventor 余长斌周永贵王杰孙蕾
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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