A kind of preparation method of boron-containing indolinone derivative

A technology for indolinone and derivatives, which is applied in the field of catalytic synthesis and achieves the effects of simple reaction raw materials, easy availability of reaction raw materials, and wide universality of substrates

Active Publication Date: 2022-07-08
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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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  • A kind of preparation method of boron-containing indolinone derivative
  • A kind of preparation method of boron-containing indolinone derivative
  • A kind of preparation method of boron-containing indolinone derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Into the reaction tube were sequentially added o-iodoaniline derivative 1a (72.6 mg, 0.2 mmol), cuprous iodide (3.8 mg, 10 mol%), triphenylphosphine (10.4 mg, 20 mol%), lithium tert-butoxide (16 mg) , 1.0eq.), pinacol diboronate (101.3mg, 2.0eq.), dichloroethane (2.0mL, 0.1M), the reaction mixture was reacted at 40°C for 5min, and directly passed through a rotary evaporator after the reaction After removing the solvent, the method of column chromatography separation (petroleum ether:ethyl acetate=15:1) was used to obtain the target product compound 1 in a yield of 98%.

[0025] 1H NMR (500MHz, CDCl3) δ 7.32 (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] Into the reaction tube were sequentially added o-iodoaniline derivative 2a (88.2 mg, 0.2 mmol), cuprous bromide (5.6 mg, 20 mol%), tricyclohexylphosphine (22.4 mg, 40 mol%), 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, after the reaction was completed, it was directly removed by a rotary evaporator After solvent, the method of column chromatography separation (petroleum ether:ethyl acetate=10:1) was used to obtain the target product compound 2 in 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] Into the reaction tube were sequentially added o-iodoaniline derivative 3a (86.2 mg, 0.2 mmol), cuprous chloride (1.9 mg, 10 mol%), 1,10-phenanthroline (3.6 mg, 10 mol%), tert-butanol Sodium (28.8mg, 1.5eq.), pinacol biboronate (50.6mg, 1.0eq.), toluene (2.0mL, 0.1M), the reaction mixture was reacted at 80°C for 5min, and directly after the reaction was completed by rotary evaporation After the solvent was removed by the instrument, a column chromatography method (petroleum ether:ethyl acetate=8:1) was used to separate the target product compound 3 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 boron-containing indolinone derivatives, in particular to a method for synthesizing boron-containing indolinone derivatives through the cyclization reaction of copper-catalyzed o-iodoaniline derivatives and biboronic acid pinacol esters , belongs to the field of organic synthesis. The method uses o-iodoaniline derivatives and biboronic acid pinacol ester as raw materials, and under the catalysis of copper catalyst, through the joint action of ligands and basic compounds, in an organic solvent, the reaction is carried out at a temperature of 40-140° C. , and the boron-containing indolinone derivatives are obtained after post-treatment after the reaction. The invention uses easily prepared o-iodoaniline derivatives and commercially available pinacol esters as raw materials, and realizes the rapid construction of boron-containing indolinone derivatives by constructing one ring and two chemical bonds in one step. The reaction conditions are mild, the operation is simple, and the reaction raw materials are readily available, the substrates are widely applicable, and the target products are easily separated.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, and relates to a preparation method of a boron-containing indolinone derivative, and more particularly, to a cyclization reaction of a copper-catalyzed o-iodoaniline derivative and biboronic acid pinacol ester Methods for the synthesis of 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 synthetic organic chemists. In recent years, there have been many literature 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 ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
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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