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Preparation method of compound with nitrogen heterocyclic skeleton by Rh(III) catalysis

A technology of nitrogen heterocycles and compounds, which is applied in the field of preparation of nitrogen heterocycle skeletons assisted by self-assembly guiding groups catalyzed by Rh, can solve the problems of insufficient preparation process, complex raw materials, and insufficient universality of substrates, etc., and achieve The raw materials are easy to obtain, the operation is simple, and the catalytic system is simple and mild.

Active Publication Date: 2019-01-18
ZHEJIANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although this work has broadened the substrate category, and has good applicability to heterocycles such as thiophene, furan, and pyridine, and the reaction conditions have become milder, the universality of the substrate is still not wide enough, and the raw materials More complicated, the preparation process is not simple enough

Method used

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  • Preparation method of compound with nitrogen heterocyclic skeleton by Rh(III) catalysis
  • Preparation method of compound with nitrogen heterocyclic skeleton by Rh(III) catalysis
  • Preparation method of compound with nitrogen heterocyclic skeleton by Rh(III) catalysis

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Experimental program
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Embodiment 1

[0042] In a 25mL Schlenk bottle, weigh 24mg (0.2mmol) p-tolualdehyde (1.5eq), Cu(OAc) 253mg (2.0eq), 2-aminopyridine 25mg (2.0eq), [Cp*RhCl2]2 3 mg (2%). Then it was vacuumized and nitrogen gas was introduced. After three operations, 2 mL of acetonitrile was added, stirred for 10 min, and then 45 μL (2.0 eq) of ethyl acrylate was added, and stirred at 80° C. in a nitrogen atmosphere. After about 5 hours, TLC detected that the reaction was complete. A little silica gel was added, the solvent was evaporated, solidified, and the solid was loaded as a sample for column chromatography. 55 mg of the product was obtained with a yield of 90%. The reaction formula is as follows:

[0043]

[0044] The physical properties and spectral data of the product are as follows: white solid; melting point: 90-92°C; 1 H NMR (CDCl 3 ,600MHz)δ8.54(d,J=12.6Hz,1H),8.42-8.40(m,1H),7.81-7.73(m,2H),7.39(s,1H),7.31(d,J=12Hz, 1H),7.07-7.04(m,1H),5.95-5.92(m,1H),4.12-4.08(m,2H),3.33(dd,J 1 =24Hz,J ...

Embodiment 2

[0046] In a 25mL Schlenk bottle, weigh 21mg (0.2mmol) benzaldehyde (1.0eq), Cu(OAc) 2 80mg (2.0eq), 2-aminopyridine 38mg (2.0eq), [Cp*RhCl2] 2 4.96 mg (2%). Then it was subjected to vacuum treatment and nitrogen gas was introduced. After three operations, 2 mL of acetonitrile was added, stirred for 10 min, and then 43 mL (2.0 eq) of ethyl acrylate was added, and stirred at 80° C. in a nitrogen atmosphere. After about 5 hours, TLC detected that the reaction was complete. A little silica gel was added, the solvent was evaporated, solidified, and the solid was loaded as a sample for column chromatography. 51 mg of the product was obtained with a yield of 85%. The reaction formula is as follows:

[0047]

[0048] The physical properties and spectral data of the product are as follows: white solid; melting point: 123-125°C; 1 H NMR (CDCl 3 ,600MHz)δ8.54(d,J=11.4Hz,1H),8.42(m,1H),7.92(d,J=11.4Hz,1H),7.79-7.74(m,1H),7.60(m,2H ),7.53-7.49(m,1H),7.09-7.06(m,1H),5.98(m,1H),4.11...

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Abstract

The invention discloses a preparation method of a nitrogen heterocyclic skeleton by self-assembly guiding group assisted Rh(III) catalysis, comprising the following steps: in the presence of a rhodiumcatalyst and an acetate, an aromatic aldehyde and a 2-aminopyridine are reacted in a solvent to produce an effective guiding group in situ. The guiding group is further reacted with a substituted olefin under rhodium catalysis, and after completion of the reaction, the compound of the nitrogen heterocyclic skeleton is obtained by post-treatment. The preparation method uses rhodium to catalyze, and successfully realizes the synthesis strategy of self-assembly and efficient guiding groups. The reaction starts from simpler raw materials, and synthesizes an isoindolinone skeleton and an isoquinoline structure with novel substitution characteristics in a concise and mild catalytic system. The preparation method has the advantages of simple operation, mild reaction conditions, high yield and high atomic economy.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method for building a nitrogen heterocyclic skeleton by catalyzing Rh(III) with the assistance of a self-assembly directing group. Background technique [0002] Isoindolinone (γ-lactam) is a more common and important mother nucleus. Since the α position is an N atom with a strong complexing force, there have been many reports on the use of the nitrogen atom in benzamide as the guiding atom and its participation in the formation of γ-lactam. [0003] Li Xingwei's research group first tried to use N-phenyl substituted aromatic formamide as a substrate in 2010 to react with acrylate to construct an isoindolinone skeleton (Org. Lett., 2010, 12, 5430). In the reaction, the Heck product intermediate is firstly generated, and then Michael addition occurs and cyclization occurs. However, if the aromatic ring in the substrate is a heterocycle such as furan or i...

Claims

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Application Information

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IPC IPC(8): C07D401/04
CPCC07D401/04
Inventor 张岩朱钢国朱海倩黄晨超戚佳一陈泽辉
Owner ZHEJIANG NORMAL UNIVERSITY