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A method for the highly selective reduction of alkynes to z-type alkenes

A synthesis method and olefin technology, applied in the field of organic compound synthesis, can solve problems such as few researches

Active Publication Date: 2021-08-24
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Copper catalysts exhibit broad functional group tolerance in such reactions and are a promising option in this regard, but little research has been done on them
The transfer hydrogenation reaction catalyzed by copper first needs to form a hydrogen-copper complex [LCu-H]. At present, the common hydrogen source is silane, hydrogen gas, ammonia borane, etc., but there is no report on the use of alcohol as the hydrogen source.

Method used

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  • A method for the highly selective reduction of alkynes to z-type alkenes
  • A method for the highly selective reduction of alkynes to z-type alkenes
  • A method for the highly selective reduction of alkynes to z-type alkenes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032]

[0033] 0.02 mmol chloride (2 mg), 0.03 mmol 1,3-bis (2,4,6-trimethyl) chlorinated (10.3 mg), 0.2 mmol of tert-butoxide (22.4 mg) In the Schlenk reaction tube, the vacuum was evacuated, and the nitrogen was charged 3 times, 1 ml of ethanol was added as a solvent, and stirred at room temperature for 15 min. 0.2 mmol of diphenyl acetylene (35.6 mg) and 0.24 mmol of boronic acid-cell acid-torubol ester (61 mg) were added to 2 ml of ethanol, and then added dropwise to the reaction tube, and the reaction was stirred at room temperature for 5 hours. After the reaction, 100-200 mesh chromatographic silica gel was added to the obtained reaction mixture and the solvent was evaporated to remove the resulting crude product, and the obtained crude product was separated, and the volume ratio of 50: 1 petroleum ether and acetate The mixture of esters is eluted as the eluent, and the TLC tracks the elution process, and the eluent containing the target product is collected, and the elue...

Embodiment 2

[0036]

[0037] 0.01 mmol of chloride (1 mg), 0.02 mmol 1,3-bis (2,4,6-trimethylphenyl) chlorinated (6.9 mg), 0.2 mmol of tert-butoxide (22.4 mg) In the Schlenk reaction tube, the vacuum was evacuated, and the nitrogen was charged 3 times, 1 ml of ethanol was added as a solvent, and stirred at room temperature for 15 min. 0.2 mmol of diphenyl acetylene (35.6 mg) and 0.24 mmol of boric acid-ravate (61 mg) were dissolved in 2 ml of ethanol, and then added to the reaction tube, and the mixture was stirred at room temperature for 5 hours. After the reaction, 100-200 mesh chromatographic silica gel was added to the obtained reaction mixture and the solvent was evaporated to remove the resulting crude product, and the obtained crude product was separated, and the volume ratio of 50: 1 petroleum ether and acetate The mixture of esters is eluted as the eluent, and the TLC tracks the elution process, and the eluent containing the target product is collected, and the eluent is evaporated ...

Embodiment 3

[0040]

[0041] 0.005 mmol chloride (0.5 mm), 0.01 mmol 1,3-bis (2,4,6-trimethylphenyl) chlorosolium chlorolium (3.4 mg), 0.2 mmol of tert-butoxide (22.4 mg) Add the Schlenk reaction tube, evacuate, and then charge 3 times, 1 ml of ethanol is added as a solvent, and stirred at room temperature for 15 min. 0.2 mmol of diphenyl acetylene (35.6 mg) and 0.24 mmol of boric acid-ravate (61 mg) were dissolved in 2 ml of ethanol, and then added to the reaction tube, and the mixture was stirred at room temperature for 5 hours. After the reaction, 100-200 mesh chromatographic silica gel was added to the obtained reaction mixture and the solvent was evaporated to remove the resulting crude product, and the obtained crude product was separated, and the volume ratio of 50: 1 petroleum ether and acetate The mixture of esters is eluted as the eluent, and the TLC tracks the elution process, and the eluent containing the target product is collected, and the eluent is evaporated to evaporase to o...

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Abstract

The invention discloses a method for highly selective reduction of alkynes into Z-type olefins: adding cuprous chloride, ligands and potassium tert-butoxide into a Schlenk reaction tube, vacuuming, and adding organic Solvent A, stir evenly at room temperature; then dissolve the diphenylacetylene compound shown in formula I and pinacol diborate in organic solvent B, add dropwise to the reaction tube, and stir at room temperature for 1 After ~12 hours, the resulting reaction solution is post-treated to obtain Z-type olefins and derivatives thereof shown in formula II; the ligand is 1,3-bis(2,4,6-trimethylphenyl) chloride imidazolium chloride, 1,3-bis(2,6-diisopropylphenyl) imidazolium chloride; safe and cheap ethanol as a hydrogen source; mild reaction conditions, saving energy consumption; in addition, it also has high yield , high selectivity, strong substrate universality, easy operation and so on.

Description

[0001] (1) Technical field [0002] The present invention relates to a method of synthesizing an organic compound, in particular to a method of high selectivity to a Z-type olefin in an alkyne. [0003] (2) Background [0004] Olefin compounds are an important organic synthetic intermediate, widely used in the fields of medicines, pesticides and materials sciences. They are widely used in chemical engineering for polymerization, multiplexue reactions, epoxidation, hydroformylation, hydroamine reactions, and the like. By this, the related synthetic technology of olefins has broad application prospects. [0005] At present, the most common method of synthesis of olefins reported at home and abroad is still the use of corresponding halogenated hydrocarbons or alcohols. In recent decades, the cross-coupling reaction using aryl olefins has also become an important method for complex olefins substituted with the synthetic functional group. In addition, the most important method is to redu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C15/52C07C5/09C07C25/24C07C22/08C07C17/354C07C43/215C07C41/20C07C255/50C07C253/30C07C69/76C07C67/303
CPCC07C5/09C07C17/354C07C41/20C07C67/303C07C253/30C07C2531/02C07C2531/22C07C2531/30C07C15/52C07C25/24C07C22/08C07C43/215C07C255/50C07C69/76
Inventor 刘运奎鲍汉扬刘潋滟
Owner ZHEJIANG UNIV OF TECH