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Preparation method of para-substituted aryl compound
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A compound and aryl technology, applied in the field of preparation of para-substituted aryl compounds, can solve the problems of single substrate type and poor tolerance of heterocyclic coupling substrates, and achieve high yield and wide substrate range. Effect
Active Publication Date: 2021-12-14
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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[0006] Aiming at the shortcomings of single substrate types and poor tolerance to heterocyclic coupling substrates in the prior art method for preparing para-substituted aryl compounds by para-selective substitution of mono-substituted aromatic hydrocarbons, a para-position A method for preparing substituted aryl compounds. The method uses monosubstituted aromatic hydrocarbons as substrates to construct aryl sulfonium salts in situ, and the palladium catalyst catalyzes the Suzuki-Miyaura coupling reaction of the aryl sulfonium salts constructed in situ. Para-arylation or alkenylation products of substituted arenes
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Embodiment 1
[0148]
[0149] Under nitrogenatmosphere, monosubstituted arene substrate 1a (0.5 mmol), thianthrene-S-oxide (0.6 mmol) and DCM (0.5 mL) were sequentially added to a 25 mL Schlenk tube, followed by stirring at -40°C. Slowly drip into Tf 2 After O (0.24 mmol), it was stirred at -40°C for 30 minutes, followed by 1 hour at room temperature. The solvent was spun out under reduced pressure, and the crude product was separated and purified by a preparative plate (DCM / MeOH (20 / 1)) to obtain sulfonium salt 2a. Among them, the molar ratio (p / o) of the para-substituted product (sulfonium salt 2a) to the ortho-substituted product is 95.3 / 1.0, and there is no meta-substituted product.
[0154] Under nitrogenatmosphere, monosubstituted arene substrate 1a (0.2 mmol), thianthrene-S-oxide (0.24 mmol) and DCM (1.0 mL) were sequentially added to a 25 mL Schlenk tube, followed by stirring at -40°C. Slowly drip into Tf 2 After O (0.24 mmol), it was stirred at -40°C for 30 minutes, followed by 1 hour at room temperature. Then sodiumbicarbonate (0.6mmol), arylboronic acid substrate 4k (0.3mmol), palladium catalyst (0.01mmol) (as shown in Table 1 below) were added under nitrogen atmosphere, acetone (1.0mL) was added, and the cap was tightened , stirred at room temperature for 12 hours. After the reaction was completed, a small amount of DCM was added to quench the reaction, filtered through diatomaceous earth, and the solvent was spun out under reduced pressure. The crude product was separated and purified on a preparative plate (hexane / EtOAc (20 / 1)) to obtain a white solid 3k. The sulfonium salt 2a of reaction,...
Embodiment 3
[0169]
[0170] Under a nitrogen atmosphere, monosubstituted arene substrate 1a (0.5 mmol), phenoxathione-10-oxide, and DCM (0.5 mL) were added sequentially to a 25 mL Schlenk tube, followed by stirring at -40°C. After slowly dropping Tf2O (0.24 mmol), it was stirred at -40°C for 30 minutes, and then stirred at room temperature for 1 hour. The solvent was spun out under reduced pressure, and the crude product was separated and purified by a preparative plate (DCM / MeOH (20 / 1)) to obtain sulfonium salt 2b. Among them, the molar ratio (p / o) of the para-substituted product (sulfonium salt 2b) to the ortho-substituted product is 76.8 / 1.0, and there is no meta-substituted product.
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Abstract
The invention discloses a preparation method of a para-substituted aryl compound as shown in formula (I), which is characterized in that it comprises the following steps: under an inertatmosphere, in a solvent, under the action of a base and a palladium catalyst, as shown in the formula The coupling reaction between the arylsulfonium salt represented by (II) and the boride represented by formula (III) can be carried out. The method uses monosubstituted aromatic hydrocarbons as substrates to construct arylsulfonium salts in situ, and palladium catalysts catalyze the Suzuki-Miyaura coupling reaction of the in situ constructed arylsulfonium salts to quickly and efficiently construct monosubstituted aromatic hydrocarbons para-arylation or alkenes. Kylation product. The method has mild conditions, high substrate universality, and wide tolerance of heterocycle-coupled substrates.
Description
technical field [0001] The invention relates to a preparation method of a para-substituted aryl compound. Background technique [0002] Para-substituted aryl compounds are widely found in natural products, active drug molecules and pesticides. For example: losartan is an antihypertensive drug; canagliflozin is used to treat diabetes; celecoxib is used to treat arthritis. These active molecules all contain diaryl structures. Therefore, it is of great significance to develop simple and efficient methods to construct diaryl compounds. [0003] The traditional arylation cross-coupling reaction needs to pre-introduce active halogens or organometallic compounds at the reaction site. In comparison, the arylation reaction directly starting from the C-H bond is the most attractive and promising method. A formidable obstacle to the direct arylation of simple arenes is the precise control of site selectivity in the absence of directing groups during C–H functionalization, especially...
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