Method for preparing alpha-aryl carbonyl compound

A carbonyl compound and arylcarbonyl technology, which is applied in the field of preparation of α-arylcarbonyl compounds, can solve the problems of narrow substrate range and inability to contain β hydrogen, and achieve the effects of easy preparation, mild reaction conditions and stable substrates

Inactive Publication Date: 2008-04-09
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in their system, the scope of substrates is narrow, and the α-position of bromoesters and amides cannot contain β-hydrogens and active hydrogens on the amide nitrogen.

Method used

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  • Method for preparing alpha-aryl carbonyl compound
  • Method for preparing alpha-aryl carbonyl compound
  • Method for preparing alpha-aryl carbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1: Reaction of 2-Bromoesters or Amides

[0017] In a reaction system, add phenylboronic acid (243.8mg, 2.0mmol), 2-bromo ester or amide (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (849.2 mg, 4.0 mmol), the system was replaced by nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. The product 2-phenyl ester or amide was obtained by column chromatography, and the separation yield is shown in Table 1 below.

[0018]

[0019] Table 1 Arylation reaction of phenylboronic acid with 2-bromoester and amide

[0020]

Embodiment 2

[0022] In a reaction system, add substituted phenylboronic acid (2.0mmol), 2-bromo ester or amide (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (849.2 mg, 4.0 mmol), the system was replaced by nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. The product 2-substituted phenyl ester or amide was obtained by column chromatography, and the separation yield is shown in Table 2 below.

[0023]

[0024] Table 2 Reaction of substituted phenylboronic acids with 2-bromo esters and amides

[0025]

[0026] b The reaction temperature is 80 degrees Celsius

Embodiment 3

[0027] Embodiment 3: the reaction of 2-bromoketone or 2-chloroketone

[0028] In a reaction system, add arylboronic acid (2.0mmol), 2-bromoketone or 2-chloroketone (1.0mmol), Ni(PPh 3 ) 4 (110.8 mg, 0.1 mmol), K 3 PO 4 (1273.8 mg, 6.0 mmol), the system was replaced with nitrogen protection, 2 ml of toluene was added, and the reaction was carried out at 60 degrees Celsius for 16 hours. Stop the reaction, add 2 ml of 2M dilute hydrochloric acid to the system, add 5-10 ml of ethyl acetate three times for extraction, combine the organic phases, and dry over anhydrous sodium sulfate. 2-aryl ketone was obtained by column chromatography. The separation yield is shown in Table 3 below.

[0029]

[0030] Table 3: Nickel-catalyzed arylation of ketones

[0031]

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Abstract

The invention relates to a method of preparing alpha-aryl carbonyl compound. With the catalyst of four triphenylphosphine nickel or acetylacetone nickel ligand, the aryl boric acid, the alpha-halogenated carbonyl compound, the ligand and the additive are dissolved in toluene, and after reaction for 10 to 24 hours in 50 to 100 DEG C, the alpha-aryl carbonyl compound is obtained, wherein, the ligand is single-tooth phosphine ligand or double-tooth phosphine ligand; and the additive is absolute potassium phosphate or tri-potassium phosphate. The invention, which utilizes the catalyst with low cost, stable substrate, easy obtaining and gentle reaction conditions, can not only catalyze arylation of ester, amide and ketone, but also can be compatible with beta hydrogen, thereby greatly expanding the range of the substrate. Moreover, the invention possesses great application potential and can directly constitute the main framework of the steride.

Description

technical field [0001] The present invention relates to a process for the preparation of α-arylcarbonyl compounds. Background technique [0002] The α-arylation of carbonyl compounds is an interesting and challenging reaction. Its α-aryl derivatives are important structural units of many natural products, drugs, and synthetic intermediates. For example, α-aryl carboxylic acid compounds such as Naproxen, flurbiprofen, and diclofenac have anti-inflammatory and analgesic effects. In this field, Buchwald, Hartwig, Gooβen and others have carried out more characteristic research. They all use palladium as a catalyst. Buchwald and Hartwig use the Reformatsky reagents of enol metal salts, enol siloxy ethers of esters or amides generated by carbonyl compounds under the action of strong bases to undergo palladium-catalyzed coupling reactions with halogenated aromatics to generate α-arylated product. From the initial ketones to the derivatives of carbonyl compounds such as nitro co...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07B41/08C07B41/12C07C69/612C07C233/11C07C49/76B01J31/24B01J31/28
Inventor 雷爱文刘超
Owner WUHAN UNIV
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