A kind of highly enantioselective 1,1-diarylborated alkane compound and its preparation method

A technology for diarylboronated alkanes and compounds, which is applied in the field of high corresponding selectivity 1,1-diarylboronated alkanes and their preparation, and can solve problems such as no literature reports.

Inactive Publication Date: 2019-04-16
NORTHEAST NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

So far, the reaction of 1,1-diaryl alkanes with high enantioselective borylation has not been reported in the literature

Method used

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  • A kind of highly enantioselective 1,1-diarylborated alkane compound and its preparation method
  • A kind of highly enantioselective 1,1-diarylborated alkane compound and its preparation method
  • A kind of highly enantioselective 1,1-diarylborated alkane compound and its preparation method

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preparation example Construction

[0036] The present invention also provides a method for preparing high enantioselectivity 1,1-diarylborated alkane compounds, the method comprising:

[0037] Step 1: reacting diaryl ketone, Wittig reagent and n-butyllithium in a polar solvent to obtain 1,1-diarylethene compound;

[0038] Step 2: Add catalyst, ligand ((2S,4S)-(-)-2,4-bis(diphenylphosphonium)pentane), counter ion and alkali to the reaction device, and then add the obtained 1,1-Diarylethene compound reacts with diboronic acid pinacol ester to obtain 1,1-diarylborated alkanes with high enantioselectivity.

[0039] According to the present invention, add Wittig reagent and polar solvent in the reaction device, preferably lower the temperature of the reaction device to -78°C, then add n-butyllithium dropwise, after the dropwise addition, preferably react at room temperature for 30min, then in the reaction device Add diaryl ketone to the mixture, preferably react at room temperature for 24 hours, TLC detects that th...

Embodiment 1

[0047] 1) Preparation of 1,1-diarylethene 1a

[0048]

[0049] To a 25 mL round bottom flask equipped with a magnetic stirrer was added methyltriphenylphosphine bromide (2.6 mmol) and tetrahydrofuran (5 mL). Move the reaction to -78°C, add n-butyllithium (2.6mmol) dropwise to the system, after the dropwise addition, react at room temperature for half an hour, then add diaryl ketone (2mmol) to the system, stir at room temperature for 24h, TLC The detection substrate disappears and the reaction ends. Pour saturated ammonium chloride aqueous solution (10mL) into the reaction, extract with dichloromethane (3×10mL), combine the organic phases, dry over anhydrous sodium sulfate, filter with suction, then distill under reduced pressure to remove the organic solvent, pass through a silica gel column layer Analysis (eluent is V 石油醚 :V 乙醚 =20:1), a colorless oily liquid was obtained, the structure of the product was confirmed to be 1a by NMR and MS, and the yield was 90%.

[0050...

Embodiment 2

[0057] 1) Preparation of 1,1-diarylethene 1b

[0058]

[0059] Under nitrogen protection, methyltriphenylphosphine bromide (2.6 mmol) and tetrahydrofuran (5 ml) were added to a 25 mL round bottom flask equipped with a magnetic stirring device. Move the reaction to -78°C, add n-butyllithium (2.6mmol) dropwise to the system, after the dropwise addition, react at room temperature for half an hour, then add diaryl ketone (2mmol) to the system, stir at room temperature for 24h, TLC The detection substrate disappears and the reaction ends. Pour saturated ammonium chloride aqueous solution (10mL) into the reaction, extract with dichloromethane (3×10mL), combine the organic phases, dry over anhydrous sodium sulfate, filter with suction, then distill under reduced pressure to remove the organic solvent, pass through a silica gel column layer Analysis (eluent is petroleum ether) to obtain a colorless oily liquid, the structure of the product was confirmed to be 1b by NMR and MS, and...

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Abstract

The invention provides high-enantioselectivity 1,1-diarylboroalkanes and a preparation method thereof, belonging to the technical field of organic synthetic chemistry. The structural general formula of the compounds is disclosed as Formula I. The invention also provides a preparation method of the high-enantioselectivity 1,1-diarylboroalkanes. The method comprises the following steps: carrying out reaction on a copper salt and an alkali under the catalytic action of an alkali to generate a tert-butyl oxy copper intermediate, and reacting with pinacol biborate to generate a copper-boron material, inserting C-C double bonds, and obtaining the hydrogen bononization products under the action of alcohol. The 1,1-diarylboroalkanes have high enantioselectivity; and the high performance liquid chromatography experiment proves that the ee value can reach 90% or above.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and in particular relates to a high enantioselective 1,1-diarylborated alkane compound and a preparation method thereof. Background technique [0002] The tertiary carbon structure of chiral asymmetric bisaryl or aralkyl groups is ubiquitous in a large number of biologically active species or drug molecules, for example, cyanaldehyde, (R)-tolterodine, podophyllin, butyl Benmorphine, etc., make it play a very important role in medicinal chemistry, biochemistry and material science. Therefore, the development of high enantioselective 1,1-disubstituted alkane compounds has important research value (Schmidt, F.; Stemmler, R.T.; Rudolph, J.; Bolm, C.Chem.Soc.Rew .2006, 35, 454.). [0003] In recent years, transition metals Rh, Co, Ir, Fe, Cu catalyzed hydroboration reactions of alkenes have attracted much attention, and a large number of literatures on the synthesis of correspond...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 熊涛张前王子宁张鸽
Owner NORTHEAST NORMAL UNIVERSITY
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