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Method for realizing N-alpha site arylation of nitrogen-containing heterocyclic ring by photocatalysis

A nitrogen-heterocyclic, photocatalytic technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve problems such as inability to achieve high efficiency, green and mild reaction conditions, and good substrate universality Effect

Pending Publication Date: 2022-07-29
HARBIN INST OF TECH SHENZHEN GRADUATE SCHOOL
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The present invention will solve the current C(sp 3 )-H functionalization technical problems, and provide a photocatalytic realization of nitrogen-containing heterocycle N-alpha position arylation method

Method used

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  • Method for realizing N-alpha site arylation of nitrogen-containing heterocyclic ring by photocatalysis
  • Method for realizing N-alpha site arylation of nitrogen-containing heterocyclic ring by photocatalysis
  • Method for realizing N-alpha site arylation of nitrogen-containing heterocyclic ring by photocatalysis

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specific Embodiment approach 1

[0032] Embodiment 1: A photocatalytic method for arylation of nitrogen-containing heterocycles at N-α position in this embodiment includes the following steps:

[0033] First, the brominated aromatic compounds, nitrogen-containing heterocyclic compounds, Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 , nickel chloride, 4,4-di-tert-butyl-2,2-bipyridine and alkali are added to the mixed solvent to obtain a mixed solution;

[0034] 2. Under the condition of inert atmosphere and room temperature, use the light source to irradiate the mixed solution obtained in step 1 for 12-20h;

[0035] 3. The mixed solution treated in the second step is subjected to rotary evaporation to remove the solvent, and then separated and purified by thin-layer chromatography. The obtained product is a nitrogen-containing heterocyclic N-α position aryl compound, and the preparation is completed.

specific Embodiment approach 2

[0036] Embodiment 2: The difference between this embodiment and Embodiment 1 is that the brominated aromatic hydrocarbon compounds in step 1 are 4-bromoacetophenone, p-trifluoromethyl bromobenzene, p-methoxybromobenzene, p-bromobenzene Benzaldehyde, p-bromophenylacetonitrile, 2-trifluoromethyl-4-bromopyridine or 2-fluoro-4-bromopyridine. Others are the same as the first embodiment.

specific Embodiment approach 3

[0037] Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the nitrogen-containing heterocyclic compounds in step 1 are N-Boc-pyrrolidine, N-Piv-pyrrolidine, N-Ac-pyrrolidine , N-Cbz-pyrrolidine, N-benzoylpyrrolidine, N-Boc-piperidine, N,N-dimethylpropionamide, N-Boc-cycloheptylamine or N-Boc-3-fluoro-pyrrole alkyl. Others are the same as in the first or second embodiment.

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Abstract

The invention discloses a method for realizing N-alpha site arylation of a nitrogen-containing heterocyclic ring by photocatalysis, relates to the technical field of catalytic synthesis, and in particular relates to a method for realizing N-alpha site arylation of the nitrogen-containing heterocyclic ring by photocatalysis under the condition of no additional HAT reagent. The method comprises the following steps: adding a brominated aromatic compound, a nitrogen-containing compound, Ir [dF (CF3) ppy] 2 (dtbbpy) PF6, nickel chloride, 4, 4-di-tertbutyl-2, 2-dipyridyl and alkali into a mixed solvent to obtain a reaction mixed solution, and performing light source irradiation at room temperature in an inert gas atmosphere to obtain the nitrogen heterocyclic ring N-alpha-position aryl compound. The coupling of C (sp3)-C (sp2) is completed under the condition that no HAT reagent is added, and the reaction is simple and convenient; and the cheap brominated aromatic compound and the photosensitizer are used, so that the economic and environment-friendly characteristics of the reaction are reflected. The method disclosed by the invention is very simple to operate, the raw materials are commercially available, the reaction can be realized at a higher yield by using a catalytic amount of a photooxidation reduction catalyst, and the method is high in atom economy and has wide substrate universality. The method is applied to the field of organic synthesis.

Description

technical field [0001] The invention relates to the technical field of catalytic synthesis, in particular to a method for photocatalytically realizing the N-α position arylation of nitrogen-containing heterocycles under the condition of no external HAT reagent. Background technique [0002] Visible light photoredox catalysis has become an important technology in organic synthesis. This class of catalysis utilizes transition metal polypyridyl complexes that can undergo single electron transfer (SET) with common functional groups under visible light excitation, activating organic molecules for various valuable transformations. Over the past century, transition metal-catalyzed cross-coupling reactions have developed into one of the most commonly used methods in organic synthesis to construct C-C, C-N, and C-heteroatom bonds, especially many routes are catalyzed by nickel to construct C-C bonds . [0003] The functionalization of C-H bonds is an important research content in o...

Claims

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Application Information

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IPC IPC(8): C07C231/12C07C233/31C07D207/08C07D211/32C07D223/04C07D401/04
CPCC07D207/08C07D401/04C07D211/32C07D223/04C07C231/12C07C233/31Y02P20/584
Inventor 杨超姚丽娟郭林齐绪宽
Owner HARBIN INST OF TECH SHENZHEN GRADUATE SCHOOL
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