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Novel method for ruthenium-catalyzed selective boronation reaction of amides

A ruthenium-catalyzed amide and selective technology, applied in organic chemistry methods, chemical instruments and methods, organic chemistry, etc., can solve problems such as limited application value, poor atom economy, and limited reports

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Problems solved by technology

[0003] There are very limited reports on transition metal-catalyzed borylation of amides, especially N,N-disubstituted amides C(sp 3 )-H borylation reaction has only one case report (J.Am.Chem.Soc.2012,134,12924)
In 2012, Sawamura et al. used loaded heterogeneous ligands and commercial rhodium metal reagents [Rh(OMe)(COD)] 2 N-hexane and 60-100 ° C reaction can selectively obtain nitrogen atom ortho-boration products, however, the reaction system mainly has the following disadvantages: (1) N,N-dialkylbenzamide substrates are not It has been reported that the substrate has certain limitations; (2) the system needs to use very expensive metal rhodium reagents (1-5mol%) and complex ligands (2-10mol%), and the application value is limited; (3) must Better yields can only be obtained by using twice the amount of amide substrates, and the atom economy of this reaction is poor

Method used

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  • Novel method for ruthenium-catalyzed selective boronation reaction of amides
  • Novel method for ruthenium-catalyzed selective boronation reaction of amides
  • Novel method for ruthenium-catalyzed selective boronation reaction of amides

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Embodiment 1

[0019] Example 1, wherein the N,N-disubstituted amide substrate is as follows:

[0020] Amide substrate structure formula:

[0021]

[0022] In an argon glove box, add metal ruthenium complex (3.0 mg, 5.6 μmol), amide substrate (11.2 mmol), B 2 pin 2 (2.8 g, 11.2 mmol). Next, the 10 mL sealed tube was tightened and removed from the glove box, and placed in an oil bath at 120° C. for heating and stirring for 24 hours. When the reaction solution was cooled to room temperature, the reaction was quenched with ethyl acetate, and then the low-boiling point organic matter was sucked dry on a rotary evaporator. Finally, methylene bromide in an equimolar amount to the substrate was added as an internal standard to measure the NMR yield of the product, and after obtaining the NMR yield, the low-boiling organic matter in the crude product was extracted again. Purification by column separation, the eluent used is ethyl acetate:methanol=1:0-5:1. product of 1 H NMR yield: 98%, isol...

Embodiment 2

[0023] Example 2, wherein the N,N-disubstituted amide substrate is as follows:

[0024] Amide substrate structure formula:

[0025]

[0026] In an argon glove box, add metal ruthenium complex (3.0 mg, 5.6 μmol), amide substrate (11.2 mmol), B 2 pin 2 (2.8 g, 11.2 mmol). Next, the 10 mL sealed tube was tightened and removed from the glove box, and placed in an oil bath at 120° C. for heating and stirring for 24 hours. When the reaction solution was cooled to room temperature, the reaction was quenched with ethyl acetate, and then the low-boiling point organic matter was sucked dry on a rotary evaporator. Finally, methylene bromide in an equimolar amount to the substrate was added as an internal standard to measure the NMR yield of the product, and after obtaining the NMR yield, the low-boiling organic matter in the crude product was extracted again. White solid, the eluent used for passing through the column is ethyl acetate:petroleum ether=1:1-1:0. product of 1 H NMR ...

Embodiment 3

[0027] Example 3, wherein the N,N-disubstituted amide substrate is as follows:

[0028] Amide substrate structure formula:

[0029]

[0030] In an argon glove box, add metal ruthenium complex (3.0 mg, 5.6 μmol), amide substrate (11.2 mmol), B 2 pin 2 (2.8 g, 11.2 mmol). Next, the 10 mL sealed tube was tightened and removed from the glove box, and placed in an oil bath at 120° C. for heating and stirring for 24 hours. When the reaction solution was cooled to room temperature, the reaction was quenched with ethyl acetate, and then the low-boiling point organic matter was sucked dry on a rotary evaporator. Finally, methylene bromide in an equimolar amount to the substrate was added as an internal standard to measure the NMR yield of the product, and after obtaining the NMR yield, the low-boiling organic matter in the crude product was extracted again. White oil, the eluent used for passing through the column is ethyl acetate:petroleum ether=1:1-1:0. product of 1 H NMR yi...

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Abstract

The present invention relates to a novel method for ruthenium-catalyzed selective boronation reaction of amides. According to the method, a hexacoordinated metal ruthenium complex containing a norbornadiene (NBD) ligand is taken as a catalyst, an N,N-disubstituted amide and bis(pinacolato)diboron are taken as reaction substrates, and in the absence of reaction solvents and under mild reaction conditions, a carbon-hydrogen bond of methylene at the ortho position of a nitrogen atom in the N,N-disubstituted amide is selectively subjected to a boronation reaction under efficient catalysis, so thata corresponding amide borate product is obtained. Compared with currently reported methods, the novel method generally has the advantages of wide substrate applicability, low catalyst usage amount, simple operation and the like. The method of the present invention realizes for the first time a selective C(sp3)-H boronation reaction of N,N-dimethyl substituted aromatic amide derivatives. In addition, the method realizes for the first time a metal-ruthenium-catalyzed selective dehydro-boronation reaction of N,N-disubstituted amides, and provides a completely new reaction strategy for organic synthetic intermediates of amide borates.

Description

technical field [0001] The invention relates to a new method for ruthenium-catalyzed selective borylation of amides. Background technique [0002] As a common organic compound, N,N-disubstituted amides are widely found in drug molecules and natural products. Therefore, how to convert N,N-disubstituted amides into more valuable organic compounds has become a key research topic in the field of organic chemistry. In recent years, the transition metal-catalyzed functionalization of carbon-hydrogen bonds is one of the most challenging and interesting topics in organic chemistry. Among them, the metal-catalyzed carbon-hydrogen bond borylation reaction of organic molecules is one of the most important conversion reactions in the carbon-hydrogen bond functionalization, and its product organoborates are very important organic intermediates to construct new molecular systems. Therefore, if the N,N-disubstituted amide C(sp 3 )-H borylation reaction to further transform them into mor...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02C07B47/00
CPCC07B47/00C07F5/02
Inventor 姚武冰韩得满贾文平
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