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Method for catalytically preparing spiral [cyclopropane-1,3'- indole] compound

A cyclopropane and compound technology, applied in the field of isatin derivative preparation, can solve the problems of complex structure of reaction raw materials and harsh reaction conditions, and achieve the effects of simple and controllable reaction conditions, controllable process and high yield

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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  • Method for catalytically preparing spiral [cyclopropane-1,3'- indole] compound
  • Method for catalytically preparing spiral [cyclopropane-1,3'- indole] compound
  • Method for catalytically preparing spiral [cyclopropane-1,3'- indole] compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Embodiment one: catalyst [(Me 3 Si) 2 N] 3 La( mu -Cl)Li(THF) 3 Synthesis

[0039] 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%.

[0040] Other catalysts can refer to the preparation method of Example 1.

Embodiment 2

[0041] Example 2: Preparation of spiro[cyclopropane-1,3′-indole] compound by reacting N-allyl isatin, diethyl phosphite and methyl acrylate

[0042] 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%.

[0043] 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

[0046] Example 3: Preparation of spiro[cyclopropane-1,3′-indole] compound by reacting N-allyl isatin, diethyl phosphite and methyl acrylate

[0047] 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 a method for catalytically preparing a spiral [cyclopropane-1,3'- indole] compound. According to the method, silicon amino rare earth compounds of [(Me3Si)2N]3Ln(mu-Cl)Li(THF)3 is used as a catalyst for catalytically replacing isatin, phosphite ester and olefin to prepare a product through one-pot reaction; in the catalyst, (Me3Si)2N represents trimethyl silicon amino; Ln represents positive trivalent rare earth metal irons and are one kind of metal irons selected from lanthanum, samarium, gadolinium, erbium or ytterbium; mu- represents a bridge key; THF represents tetrahydrofuran. In the method, the synthesis method of the catalyst is simple; the reaction raw materials are simple and can be easily obtained; the application range of a substrate is wide; the efficiency of the one-pot reaction method is high; the reaction conditions are mild; the yield of most target products can reach 85 percent or higher.

Description

technical field [0001] The invention belongs to the technical field of preparation of isatin derivatives, in particular to a catalytic preparation method of a spiro[cyclopropane-1,3'-indole] compound. 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 arylation of cyclopropane (see Ladd, C. L.; Roman, D. ...

Claims

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Application Information

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