Synthesis method for preparing trisubstituted alkenes based on nickel catalysis

A synthesis method and tri-substituted technology are applied in the field of synthesis of single-configuration tri-substituted olefin compounds, which can solve the problems of difficulty in synthesis, limited source of raw materials, and difficulty in separation, and achieve the effects of wide sources and simple feeding methods.

Active Publication Date: 2018-01-19
CHUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The present invention aims at the problems of limited source of raw materials, difficulty in synthesis, harsh reaction conditions, low reaction area and stereoselectivity in the synthesis of trisubstituted olefins, resulting in relatively low cis-trans ratio of products and difficult separation, etc., and provides a simple nickel catalyst for reaction , a wide range of raw material sources, mild reaction conditions, and good functional group compatibility based on a nickel-catalyzed synthesis method for the preparation of trisubstituted olefins

Method used

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  • Synthesis method for preparing trisubstituted alkenes based on nickel catalysis
  • Synthesis method for preparing trisubstituted alkenes based on nickel catalysis
  • Synthesis method for preparing trisubstituted alkenes based on nickel catalysis

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Experimental program
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Effect test

Embodiment 1

[0060] Embodiment 1, the reaction formula of this embodiment is as follows:

[0061]

[0062] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (12mol%), carbonic acid Potassium (2.5 eq) was added to a branched, sealed reaction tube containing magnets, which was purged with argon three times. Under argon protection, add 0.7mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add phenylpropyne (2eq) and cyclohexyl iodide (0.2 mmol) and methyldiethoxysilane (3eq) into the reaction solution, plugged the stopcock, and placed in an oil bath at 30°C for 10 hours with stirring.

[0063] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0064] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crude product, and then purify the crude p...

Embodiment 2

[0066] The reaction formula of this embodiment is as follows:

[0067]

[0068] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (12mol%), carbonic acid Potassium (2.5 eq) was added to a branched, sealed reaction tube containing magnets, which was purged with argon three times. Under argon protection, add 0.7mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add phenylpropyne (2eq), N-(2- Add iodopropyl)-N-methylaniline (0.2mmol) and methyldiethoxysilane (3eq) into the reaction solution, stopper the stopper, place in an oil bath at 30°C and stir for 10 hours.

[0069] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0070] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crude product, and then purify the crude product wi...

Embodiment 3

[0072] The reaction formula of this embodiment is as follows:

[0073]

[0074] (1) Under air, nickel(II) diethylene glycol dimethyl ether complex (12mol%), 4,4'-di-tert-butyl-2,2'-bipyridine (12mol%), carbonic acid Potassium (2.5 eq) was added to a branched, sealed reaction tube containing magnets, which was purged with argon three times. Under argon protection, add 0.7mL N,N-dimethylacetamide to the reaction tube, stir at room temperature for 5 minutes, then add 4-octyne (2eq), 3-iodo- Add 1-p-toluenesulfonylpyrrolidine (0.2mmol) and methyldiethoxysilane (3eq) into the reaction liquid, stopper the stopper, place in an oil bath at 30°C and stir for 10 hours.

[0075] (2) Add ethyl acetate to the material obtained in step (1) and mix thoroughly, filter out the solid residue with a short silica gel column, and keep the organic phase.

[0076] (3) Spin dry the solvent in the organic phase obtained in step (2) to obtain a crude product, and then purify the crude product with...

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Abstract

The invention discloses a synthesis method for preparing trisubstituted alkenes based on nickel catalysis. An alkyl halide compound and intramolecular alkynes are used as raw materials, and under theaction of a nickel catalyst, a ligand, alkali and silane, and reaction is carried out in a solvent according to the following equation, so as to obtain a trisubstituted alkene compound having a singleconfiguration. The trisubstituted alkenes synthesized by the method disclosed by the invention have very high regioselectivity and stereospecificity, and the trisubstituted alkenes in a single configuration can be completely obtained, thereby solving the problem of mixed alkene product separation. At the same time, a reaction system has a simple feeding way and does not need to use a metal reagent sensitive to moisture and air, so as to be more convenient in actual use. The alkyl halide compound can be synthesized directly from alkyl alcohol, the intramolecular alkyne has a wide source and iseasily available. The reaction conditions are mild, some alkali-sensitive groups are well compatible, and the functional group compatibility is excellent.

Description

technical field [0001] The invention relates to the technical field of compound substance preparation, in particular to a method for synthesizing a single-configuration trisubstituted olefin compound. Background technique [0002] Alkenes are an important class of structural fragments in organic chemistry, and are widely used in materials, petrochemical and pharmaceutical industries. The research on the synthesis method of alkenes has always been the focus of people's attention. The traditional synthesis methods include elimination reaction, reduction reaction, Wittig reaction and Julia olefination reaction. These reactions generally have disadvantages such as harsh reaction conditions, high reaction temperature, and the need to use a relatively strong base in the reaction system. The most important point is that the cis-trans selectivity of the synthesized olefins is not high, resulting in difficult separation of products. [0003] In addition to the above metal-free catal...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/00C07C2/86C07C2/88C07C13/28
Inventor 陆晓雨洪美岚
Owner CHUZHOU UNIV
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