Preparation method of boron-containing indolinone derivative

A technology of indolinone and its derivatives, which is applied in the field of catalytic synthesis, and achieves the effects of simple operation, simple and easy-to-obtain raw materials, and mild conditions

Active Publication Date: 2020-04-24
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these reactions are limited to the relatively expensive metal palladium as a catalyst, so it is of great research significance to develop cheap metal salts as catalysts to realize the construction of indolinone derivatives.

Method used

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  • Preparation method of boron-containing indolinone derivative
  • Preparation method of boron-containing indolinone derivative
  • Preparation method of boron-containing indolinone derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Add o-iodoaniline derivative 1a (72.6mg, 0.2mmol), cuprous iodide (3.8mg, 10mol%), triphenylphosphine (10.4mg, 20mol%), lithium tert-butoxide (16mg , 1.0eq.), diboronic acid pinacol ester (101.3mg, 2.0eq.), dichloroethane (2.0mL, 0.1M), the reaction mixture was reacted at 40°C for 5min, and passed through the rotary evaporator directly after the reaction After removing the solvent, the target compound 1 was obtained by column chromatography (petroleum ether: ethyl acetate = 15:1) with a yield of 98%.

[0025] 1H NMR (500MHz, CDCl3) δ7.32 (t, J = 1.7Hz, 1H), 7.30 (dd, J = 11.8, 4.0Hz, 3H), 7.25 (dd, J = 9.3, 5.7Hz, 2H), 7.19 (ddd, J=8.2,4.2,1.2Hz,1H),7.08–7.03(m,1H),6.86(d,J=7.6Hz,1H),3.20(s,3H),1.92(dd,J=58.5 ,15.2Hz,2H),0.96(s,6H),0.86(s,6H).

Embodiment 2

[0027] Add o-iodoaniline derivative 2a (88.2mg, 0.2mmol), cuprous bromide (5.6mg, 20mol%), tricyclohexylphosphine (22.4mg, 40mol%), potassium tert-butoxide (44.8 mg, 2eq.), pinacol diboronate (76.0mg, 1.5eq.), dichloromethane (2.0mL, 0.1M), the reaction mixture was reacted at 60°C for 15min, and removed directly by a rotary evaporator after the reaction After the solvent, the target compound 2 was obtained by column chromatography (petroleum ether: ethyl acetate = 10:1) with a yield of 66%.

[0028] 1H NMR (500MHz, CDCl3) δ7.32–7.27(m,4H),7.25–7.20(m,2H),7.18(d,J=7.9Hz,1H),7.03(d,J=1.6Hz,1H) ,3.19(s,3H),1.91(dd,J=44.7,15.4Hz,2H),1.01(s,6H),0.91(s,6H).

Embodiment 3

[0030] In the reaction tube, add o-iodoaniline derivative 3a (86.2mg, 0.2mmol), cuprous chloride (1.9mg, 10mol%), 1,10-phenanthroline (3.6mg, 10mol%), tert-butanol Sodium (28.8mg, 1.5eq.), pinacol diborate (50.6mg, 1.0eq.), toluene (2.0mL, 0.1M), the reaction mixture was reacted at 80°C for 5min, and directly evaporated by rotary evaporation after the reaction After removing the solvent, the target compound 3 was obtained by column chromatography (petroleum ether: ethyl acetate = 8:1) with a yield of 80%.

[0031] 1H NMR (500MHz, CDCl3) δ7.62 (d, J = 7.8Hz, 2H), 7.31–7.27 (m, 4H), 7.27–7.23 (m, 1H), 6.95 (d, J = 8.2Hz, 1H) ,3.24(s,3H),1.99–1.91(m,2H),0.99(s,6H),0.89(s,6H).

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Abstract

The invention discloses a preparation method of a boron-containing indolinone derivative, particularly relates to a method for synthesizing the boron-containing indolinone derivative by catalyzing a cyclization reaction of an o-iodobenzidine derivative and bis(pinacolato)diboron through copper, and belongs to the field of organic synthesis. The method comprises the steps: taking the o-iodobenzidine derivative and bis(pinacolato)diboron as raw materials, carrying out a reaction in an organic solvent at the temperature of 40-140 DEG C under the catalysis of a copper catalyst and the combined action of a ligand and an alkaline compound, and after the reaction is finished, carrying out post-treatment to obtain the boron-containing indolinone derivative. The o-iodobenzidine derivative which iseasy to prepare and commercially available bis(pinacolato)diboron are used as raw materials, and rapid construction of the boron-containing indolinone derivative is realized through one-step construction of a ring and two chemical bonds. The method is mild in reaction condition and simple and convenient to operate, and has the advantages of easily available reaction raw materials, wide substrate applicability, easy separation of target products and the like.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, and relates to a method for preparing boron-containing indolinone derivatives, more specifically, to a copper-catalyzed cyclization reaction between o-iodoaniline derivatives and biboronic acid pinacol ester Method for synthesizing boron-containing indolinone derivatives. Background technique [0002] Heterocyclic compounds are ubiquitous in natural products and bioactive molecules, and have received extensive attention in the fields of medicine, pesticides, dyes, and biology. As an important class of heterocyclic molecules, indolinone compounds have always been one of the research objects of organic synthetic chemists. In recent years, there have been many reports on the synthesis of indolinones using different reaction strategies. Among them, based on the palladium-catalyzed series cyclization reaction strategy, the coupling reaction of o-iodoaniline derivatives through the genera...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/025Y02P20/55
Inventor 贾义霞陈如意梁仁校
Owner ZHEJIANG UNIV OF TECH
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