Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen

A cross-coupling, visible light technology, applied in the field of cross-coupling hydrogen release, visible light-catalyzed cross-coupling hydrogen release of tertiary amines and nucleophiles, can solve the problems of insufficient driving force, difficult to achieve, etc., to achieve the scope of application Wide, mild reaction conditions, efficient cross-coupling effect

Active Publication Date: 2014-06-04
TECHNICAL INST OF PHYSICS & CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
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  • Application Information

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Problems solved by technology

The most ideal way to realize the cross-coupling reaction of "atom economy" is to release a molecule of hydrogen gas while successfully building a carbon-carbon bond. Difficult to achieve
Therefore, most of the current reports are to obtain the coupling product by removing a molecule of hydrogen from the oxidant. There are no patents or literature reports on the use of visible light catalysis to achieve cross-coupling between tertiary amines and nucleophiles in an inert gas atmosphere. The reaction is accompanied by the evolution of hydrogen

Method used

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  • Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen
  • Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen
  • Method using visible light catalyzed cross-coupling reaction to prepare coupling product and release hydrogen

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Effect test

Embodiment 1

[0032] With cobalt complex 1 as catalyst, 0.36 mg of the catalyst was added to 2 mL of water; with eosinY as photosensitizer, 0.7 mg of the photosensitizer was added to 2 mL of water; the catalyst solution and the photosensitizer solution were mixed to obtain 4 mL of a mixed aqueous solution. Take 0.1mmol tertiary amine-1 (X, Y are H) and 0.2mmol indole-1 (R 1 ﹑ R 2 ﹑ R 3 ﹑ R 4 ﹑ R 5 H) was dissolved in 1 mL of acetonitrile to obtain an acetonitrile solution. Further, 4 mL of the mixed aqueous solution was added to the acetonitrile solution to obtain 5 mL of the mixed solution. Wherein the concentration of photosensitizer is 2.0×10 -4 M, the catalyst concentration is 2.0×10 -4 M. Nitrogen deoxygenated for 30 minutes, sealed with wax, injected with 600 μL of internal standard methane, and then irradiated with 525nm±10nm Green LEDs at 40°C for 12 hours, using gas chromatography (TCD as the detector, Shanghai Technology Scientific Instrument Co., Ltd., Technology 7890II T...

Embodiment 2

[0034] With embodiment 1, difference is: add 1.44mg photosensitizer, the concentration of photosensitizer is 4.0 * 10 -4 M. Approximately 315 μL of hydrogen gas was produced. The product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The conversion of the starting material was 15%, the yield of the coupling product was 11%, and the amount of hydrogen evolved was 14% relative to the theoretical value.

Embodiment 3

[0036] With embodiment 1, difference is: add 2.04mg photosensitizer, the concentration of photosensitizer is 6.0×10 -4 M. Approximately 427 μL of hydrogen gas was produced. The product is 1-(1H-indol-3-yl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The conversion of the starting material was 21%, the yield of the coupling product was 13%, and the amount of hydrogen evolved was 19% relative to the theoretical value.

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Abstract

The invention discloses a method using visible light catalyzed cross-coupling reaction to prepare a coupling product and release hydrogen. The method is as follows: a tertiary amine, a nucleophile, a cobalt complexe 1 or a cobalt complexe 2 and eosin Y are added into a solvent to obtain a mixed solution, and under the protection of an inert gas, visible light is used to irradiate the mixed solution to obtain the cross-coupling product of the tertiary amine and the nucleophile and release the hydrogen. The reaction can be achieved by visible light irradiation in the presence of the inert gas, and is mild in reaction conditions, the whole system is free of externally-applied electron donors or acceptors, and the method is energy-saving and environmentally-friendly.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis and relates to a method for cross-coupling dehydrogenation, in particular to a method for cross-coupling dehydrogenation of tertiary amines and nucleophilic reagents catalyzed by visible light. Background technique [0002] In the field of chemistry, the development of reactions with high selectivity, mild conditions, and environmental protection has always been the goal pursued by chemists. In traditional chemistry, relatively harsh conditions are often required, such as high temperature, high pressure, strong acid, strong alkali, etc. As early as a century ago, the famous photochemist Ciamician wrote an article describing and prospecting the advantages and importance of light as a clean energy source in driving chemical reactions. Since 2008, visible light-catalyzed organic reactions have achieved a series of remarkable research results. For example, the Yoon group at the Universit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D401/04C07D217/14C07F9/62C01B3/02
CPCC01B3/02C07D217/14C07D401/04C07F9/62
Inventor 吴骊珠钟建基孟庆元
Owner TECHNICAL INST OF PHYSICS & CHEMISTRY - CHINESE ACAD OF SCI
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