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Application of tris(bis(trimethylsilyl)amino)lanthanum to catalyzed preparation of spiro[cyclopropane-1,3'-indole] compound

A technology of rare earth compounds and compounds, applied in the field of preparation of isatin derivatives, can solve problems such as harsh reaction conditions and complex structure of reaction raw materials, and achieve the effects of controllable process, simple and controllable reaction conditions, and low reaction cost

Active Publication Date: 2017-02-22
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The above methods can produce spiro[cyclopropane-1,3′-indole] compounds, but there are some defects generally, such as the complex structure of the reaction raw materials requires pre-synthesis, the use of diazonium reagents, the presence of metered bases or noble metal catalysis, the reaction harsh conditions, etc.

Method used

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  • Application of tris(bis(trimethylsilyl)amino)lanthanum to catalyzed preparation of spiro[cyclopropane-1,3'-indole] compound
  • Application of tris(bis(trimethylsilyl)amino)lanthanum to catalyzed preparation of spiro[cyclopropane-1,3'-indole] compound
  • Application of tris(bis(trimethylsilyl)amino)lanthanum to catalyzed preparation of spiro[cyclopropane-1,3'-indole] compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Embodiment one: catalyst [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 Synthesis

[0041] At -10°C, a hexane solution of n-BuLi (60 mmol, 2.52 M) was slowly added to a tank containing (Me 3 Si) 2 NH (60mmol) in a 100 mL Schlenk reaction flask and reacted at room temperature for 30 minutes. The above reaction solution was added to anhydrous LaCl 3 (20 mmol) in THF (30 mL) and stirred overnight at room temperature. The solvent was removed under reduced pressure, and the obtained solid powder was extracted with hot toluene to remove LiCl, concentrated, placed at 0°C, and a large number of crystals were precipitated, which was the desired lanthanum siliconamide compound, with a yield of 85%.

[0042] Other catalysts can refer to the preparation method of Example 1.

Embodiment 2

[0043] Example 2: Preparation of spiro[cyclopropane-1,3′-indole] compound by reacting N-allyl isatin, diethyl phosphite and methyl acrylate

[0044] In the reaction flask treated with dehydration and deoxygenation, weigh [(Me 3 Si) 2 N] 3 Yb( mu -Cl)Li(THF) 3 (0.1506 g, 0.165 mmol), followed by adding acetonitrile (0.5 mL), diethyl phosphite (0.6 mmol), N-allyl isatin (0.0936 g, 0.5 mmol), acetonitrile (0.5 mL), methyl acrylate (1.5 mmol), mixed and stirred at room temperature for 5 hours, adding water to terminate the reaction, extracted three times with ethyl acetate, dried the extract with anhydrous sodium sulfate, filtered, removed the solvent under reduced pressure, and finally subjected to flash column chromatography on silica gel ( Eluent: ethyl acetate:petroleum ether=1:7) to obtain a colorless oily product with a yield of 84%.

[0045] The theoretical molecular formula of the obtained product and the main NMR test data are as follows. It can be seen from the ana...

Embodiment 3

[0048] Example 3: Preparation of spiro[cyclopropane-1,3′-indole] compound by reacting N-allyl isatin, diethyl phosphite and methyl acrylate

[0049] In the reaction flask treated with dehydration and deoxygenation, weigh [(Me 3 Si) 2 N] 3 Er( mu -Cl)Li(THF) 3 (0.1497 g, 0.165 mmol), followed by adding acetonitrile (0.5 mL), diethyl phosphite (0.6 mmol), N-allyl isatin (0.0936 g, 0.5 mmol), acetonitrile (0.5 mL), methyl acrylate (1.5 mmol), mixed and stirred at room temperature for 5 hours, adding water to terminate the reaction, extracted three times with ethyl acetate, dried the extract with anhydrous sodium sulfate, filtered, removed the solvent under reduced pressure, and finally subjected to flash column chromatography on silica gel ( Eluent: ethyl acetate:petroleum ether=1:7) to obtain a colorless oily product with a yield of 68%.

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Abstract

The invention discloses application of tris(bis(trimethylsilyl)amino)lanthanum to catalyzed preparation of a spiro[cyclopropane-1,3'-indole] compound. The chemical formula of tris(bis(trimethylsilyl)amino)lanthanum is [(Me3Si)2N]3Ln(Mu-Cl)Li(THF)3, and can be taken as a catalyst for catalyzing substitution of isatin, phosphite ester and olefin to prepare the spiro[cyclopropane-1,3'-indole] compound through a one-pot reaction; in the catalyst, (Me3Si)2N represents trimethylsilylamino; Ln represents positive trivalent rare earth metal ions, and is selected from one of lanthanum, samarium, gadolinium, erbium or ytterbium; Mu- represents a bridged bond; THF represents tetrahydrofuran. In the method, a catalyst synthesizing method is simple, reaction raw materials are simple and readily available, a substrate has a wide application range, the one-pot reaction has high efficiency, reaction conditions are mild, and the yields of most target products are 85 percent or more.

Description

technical field [0001] The invention belongs to the technical field of preparation of isatin derivatives, and specifically relates to the application of a rare earth silamide in the catalytic preparation of spiro[cyclopropane-1,3'-indole] compounds. Background technique [0002] The spiro[cyclopropane-1,3′-indole] skeleton widely exists in many natural products and drug molecules, and some herbicides, inhibitors and antagonists that have been applied use it as the main structural unit. In addition, the spiro[cyclopropane-1,3′-indole] skeleton is also used as an intermediate for the synthesis of some important alkaloids. Therefore, it is of great theoretical and practical significance to study the efficient synthesis technology of spiro[cyclopropane-1,3′-indole] skeleton. [0003] In the prior art, the reported synthetic routes of the spiro[cyclopropane-1,3′-indole] skeleton are relatively limited, mainly including four types of methods. First, Pd catalyzes the direct aryla...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07D209/96
CPCB01J31/1805B01J31/2208B01J2531/0219B01J2531/11B01J2531/37C07D209/96
Inventor 徐凡彭程翟娇娇
Owner SUZHOU UNIV
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