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Chiral phosphorous ligand as well as metal catalyst containing ligand and application of chiral phosphorous ligand and catalyst

A technology of ligand compounds and transition metals, applied in the field of gossypol synthesis, can solve the problems of poor reaction selectivity and low yield, etc.

Inactive Publication Date: 2015-05-27
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, this kind of sterically hindered substituted aryl structure is mainly obtained through several steps of Friedel-Crafts acylation. This method has poor reaction selectivity and low yield.

Method used

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  • Chiral phosphorous ligand as well as metal catalyst containing ligand and application of chiral phosphorous ligand and catalyst
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  • Chiral phosphorous ligand as well as metal catalyst containing ligand and application of chiral phosphorous ligand and catalyst

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preparation example Construction

[0216] Preparation method of bidentate phosphine-phosphine oxygen ligand compound

[0217] The present invention also provides a preparation method of the bidentate phosphine-phosphine oxygen ligand compound shown in formula I,

[0218]

[0219] The method comprises the steps of:

[0220] (a) in an organic solvent, the compound of formula e is selectively reduced to a single phosphine-oxygen double bond, thereby forming a bidentate phosphine-phosphine-oxygen ligand compound shown in formula I,

[0221]

[0222] In each formula, R, R' and R" are as defined above.

[0223] Typically, the organic solvent in step (a) includes (but not limited to): toluene, tetrahydrofuran, anhydrous diethyl ether, or a combination thereof.

[0224] In another preferred embodiment, the reaction temperature in step (a) is 40-100°C, preferably 50-90°C, more preferably 60-90°C.

[0225] In another preferred embodiment, the reaction time of step (a) is 3-48 hours, preferably 5-24 hours, more p...

Embodiment 1

[0328] Preparation of bidentate phosphine-phosphine oxygen ligand compound L4

[0329]

[0330] 1. Synthesis of compound b

[0331] Compound a (1.23g, 8.15mmol, 1.1equiv) was dissolved in 15mL of tetrahydrofuran, cooled to 0°C, n-butyllithium (3.20mL, 8.15mmol, 1.1equiv) was slowly added dropwise, and stirred at 0°C for 1 hour. Then slowly add tert-butylphosphorous dichloride (1.18g, 7.41mmol, 1.0equiv) dissolved in tetrahydrofuran (15mL) to the reaction system at 0°C, move the reaction system to room temperature and stir for 4 hours before adding 3mL water, reacted at room temperature for 3 hours. At room temperature, sodium hydroxide solution (2M, 7.4mL, 14.82mmol, 2.0equiv) and formaldehyde solution (37%, 1.60mL, 3.0equiv) were added dropwise to the reaction system to ensure that the temperature of the system was always lower than 30°C. Afterwards, the reaction system was stirred at room temperature for 3 hours. Add dilute hydrochloric acid (6M) to the reaction system...

Embodiment 2

[0346] Preparation of bidentate phosphine-phosphine oxygen ligand compound L3

[0347]

[0348] 1. Synthesis of Ligand L3

[0349] Compound f (0.38 g, 1.00 mmol, 1.0 equiv) was put into a Schlenk tube, and toluene (5 mL) was added after pumping nitrogen three times. Add HSiCl to this reaction system 3 (0.51 ml, 5.00 mmol, 5.0 equiv) and TEA (1.40 mL, 10.00 mmol, 10.0 equiv). The reaction system was stirred at 80° C. for 12 hours, cooled to room temperature, and the toluene was vacuum-dried. Add 30% sodium hydroxide aqueous solution (20mL) dropwise to the reaction system, hydrogen gas is generated during the dropwise addition, the reaction system is heated and stirred at 60°C for 30 minutes and then cooled to room temperature, and MTBE (20mL×3 ) extraction, the combined organic phases were added to dry over anhydrous sodium sulfate. Filtered and dried by pumping through a neutral alumina column to obtain white solid L3 (0.35g, 0.91mmol, 96%).

[0350] Ligand L3: 1 H NM...

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Abstract

The invention relates to a chiral phosphorous ligand as well as a metal catalyst containing the ligand and an application of the chiral phosphorous ligand and the catalyst, and particularly discloses a bidentate phosphine-phosphonate ligand compound or an enantiomer, a despinner or a diastereoisomer thereof, wherein the bidentate phosphine-phosphonate ligand compound has a structure as shown in formula I in the specification. The invention further discloses a transition metal catalyst containing the bidentate phosphine-phosphonate ligand compound and an application of the transition metal catalyst to catalyzing coupling reaction for synthesizing noncyclic alkyl aromatic hydrocarbon.

Description

technical field [0001] The present invention relates to the field of metal catalysts. More specifically, the present invention relates to novel bidentate phosphine-phosphine oxygen ligand compounds and metal catalysts containing the ligand compounds and their Suzuki- Miyaura coupling reaction and its application in a new method for the synthesis of gossypol. Background technique [0002] The direct coupling of carbon-carbon bonds catalyzed by transition metals is an important method for the synthesis of a series of alkyl-substituted aromatic compounds, and it is widely used in pharmaceutical research. However, the existing methods still have great limitations for large steric hindrance carbon-carbon bond coupling, and the applicable high-efficiency catalysts and ligands are still rare. Especially for the formation of carbon-carbon bonds between bulky aryl groups and alkyl groups, there is a lack of efficient methods. The main reason is the presence of β-hydrogen in the alk...

Claims

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Application Information

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IPC IPC(8): C07F9/6571C07F15/00B01J31/22C07B37/00C07J1/00C07C303/30C07C309/65C07C41/18C07C43/20C07C45/68C07C47/575
Inventor 汤文军李承喜
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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