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Preparation method trans-tetra-substituted alkene derivative

A technology of tetrasubstituted and derivatives, which is applied in the field of preparation of trans tetrasubstituted olefin derivatives, can solve problems such as theoretical difficulties, and achieve the effects of wide substrate range, simple post-treatment, and strong reaction specificity

Active Publication Date: 2019-06-14
HUAQIAO UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The construction of tetrasubstituted alkenes by carbometallation of internal alkynes is the most effective method, but this type of reaction can only obtain cis tetrasubstituted alkenes (Org. Lett. 2003, 5, 1579.)
For the synthesis of trans tetrasubstituted alkenes, there are still theoretical difficulties

Method used

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  • Preparation method trans-tetra-substituted alkene derivative
  • Preparation method trans-tetra-substituted alkene derivative
  • Preparation method trans-tetra-substituted alkene derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Preparation of (Z)-4,4'-(1-(o-tolyl)-2-(p-tolyl)ethylene-1,2-diyl)bis(methoxybenzene)

[0025]

[0026] 0.3mmol of sodium carbonate, 0.1mmol of 1,2-bis(4-methoxyphenyl)acetylene, 0.005mmol of tetrakistriphenylphosphine palladium, 0.005mmol of bis(2-diphenylphosphophenyl) ether, 4- Add 0.2mmol of methylphenylboronic acid, 0.3mmol of 2-isopropyl iodobenzene and 1mL of N,N-dimethylformamide into a 15mL reaction tube, fill it with nitrogen gas repeatedly 10 times, and place it in an oil bath at 120°C. Reacted for 24h; cooled to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, and the organic phase was washed with anhydrous Na 2 SO 4 Drying, filtration, concentration, and purification by thin-layer chromatography gave 34.9 mg of the target product with a yield of 78%. The NMR and high-resolution mass spectrometry of this compound are characterized as follows: 1 H NMR (500MHz, CDCl 3 )δ7.17-7.12(m, 2H), 7.03-6.93(m,...

Embodiment 2

[0028] (Z)-4,4'-(1-(2-(methoxymethyl)phenyl)-2-(p-tolyl)ethylene-1,2-diyl)bis(methoxybenzene) preparation

[0029]

[0030] 0.3mmol of sodium carbonate, 0.1mmol of 1,2-bis(4-methoxyphenyl)acetylene, 0.005mmol of tetrakistriphenylphosphine palladium, 0.005mmol of bis(2-diphenylphosphophenyl) ether, 4- Add 0.2mmol of methylphenylboronic acid, 0.3mmol of 1-iodo-2-(methoxymethyl)benzene and 1mL of N,N-dimethylformamide into a 15mL reaction tube, fill it with nitrogen gas repeatedly 10 times, and place In an oil bath at 120°C, react for 24 hours; cool to room temperature, dilute the reaction solution with ethyl acetate, wash with water three times, and wash the organic phase with anhydrous Na 2 SO 4 Drying, filtration, concentration, and purification by thin-layer chromatography gave 22 mg of the target product, with a yield of 49%. The NMR and high-resolution mass spectrometry of this compound are characterized as follows: 1 H NMR (500MHz, CDCl 3 )δ7.30 (dd, J = 7.8, 1.3 H...

Embodiment 3

[0032] Preparation of (Z)-4,4'-(1-(2-fluorophenyl)-2-(p-tolyl)ethylene-1,2-diyl)bis(methoxybenzene)

[0033]

[0034] 0.3mmol of sodium carbonate, 0.1mmol of 1,2-bis(4-methoxyphenyl)acetylene, 0.005mmol of tetrakistriphenylphosphine palladium, 0.005mmol of bis(2-diphenylphosphophenyl) ether, 4- Add 0.2mmol of methylphenylboronic acid, 0.3mmol of 2-fluoroiodobenzene and 1mL of N,N-dimethylformamide into a 15mL reaction tube, fill it with nitrogen gas repeatedly 10 times, place it in an oil bath at 120°C, and react for 24h ; Cooled to room temperature, the reaction solution was diluted with ethyl acetate, washed three times, and the organic phase was washed with anhydrous Na 2 SO 4 Drying, filtration, concentration, and purification by thin-layer chromatography gave 19.9 mg of the target product, with a yield of 47%. The NMR and high-resolution mass spectrometry of this compound are characterized as follows: 1 H NMR (500MHz, CDCl 3 )δ7.11-7.03(m, 3H), 6.97-6.90(m, 10H), 6...

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Abstract

The invention discloses a preparation method of a trans-tetra-substituted alkene derivative. The preparation method comprises following steps: 1, an alkali, an alkyne, a palladium catalyst, a ligand,a halogenated aromatic hydrocarbon, a precursor compound, and an organic solvent are introduced into a reaction container, nitrogen gas is adopted for repeat filling, and reaction is carried out for 12 to 36h at 80 to 140 DEG C; 2, a product obtained in step 1 is diluted with ethyl acetate, is washed with water, and is separated so as to obtain an organic phase; and 3, the organic phase obtained in step 2 is subjected to drying, filtering, concentrating, and column chromatography or thin-layer chromatography processing so as to obtain the trans-tetra-substituted alkene derivative. According tothe preparation method, a tetra-aromatic hydrocarbon-substituted trans-tetra-substituted alkene and a tri-aromatic hydrocarbon and a trimethylsilane-substituted trans-tetra-substituted alkene can beobtained at the same time, excellent zone selectivity is achieved, and the trans-tetra-substituted alkene derivative which is not easily synthesized using other methods is synthesized.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of trans tetrasubstituted olefin derivatives. Background technique [0002] Tetrasubstituted alkenes widely exist in synthetic compounds and natural products, and have unique optical, electrical and pharmaceutical properties. Among the most representative molecules are tetraaryl substituted alkenes. This class is widely used in molecular devices, liquid crystal materials, chemical sensors and biological imaging and other fields. Tetrasubstituted alkenes also appear in the anticancer drugs tamoxifen, idoxifene and etacstil, and in the estrogen receptor modulator GDC-0810. In addition, tetrasubstituted alkenes are important synthetic starting materials for a variety of asymmetric reactions, including dihydroxylation, epoxidation, and hydrogenation. The chiral products obtained by such reactions often retain the stereostructure informati...

Claims

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Application Information

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IPC IPC(8): C07C1/32C07C41/30C07C67/343C07C303/40C07D295/096C07D317/54C07D333/08C07F7/08C07C43/205C07C43/225C07C43/23C07C69/94C07C15/52C07C311/17C07B37/04
Inventor 程国林吕薇薇
Owner HUAQIAO UNIVERSITY
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