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Method for highly selectively reducing alkyne to generate Z-olefin

A high-selectivity, synthetic method technology, applied in the field of organic compound synthesis, can solve problems such as few researches, and achieve the effects of high selectivity, high yield and mild reaction conditions

Active Publication Date: 2019-03-05
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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  • Method for highly selectively reducing alkyne to generate Z-olefin
  • Method for highly selectively reducing alkyne to generate Z-olefin
  • Method for highly selectively reducing alkyne to generate Z-olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029]

[0030] 0.02mmol cuprous chloride (2mg), 0.03mmol 1,3-bis(2,4,6-trimethylphenyl) imidazolium chloride (10.3mg), 0.2mmol potassium tert-butoxide (22.4mg) Put it into a Schlenk reaction tube, vacuumize it, and replace the nitrogen three times, add 1ml of ethanol as a solvent, and stir at room temperature for 15 minutes. Then 0.2 mmol of diphenylacetylene (35.6 mg) and 0.24 mmol of diboronic acid pinacol ester (61 mg) were dissolved in 2 mL of ethanol, and then added dropwise into the reaction tube, and stirred at room temperature for 5 hours. After the reaction was finished, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure. The mixture of esters is used as the eluent for elution, and the elution process is tracked by TLC, the eluent containing the target product is collected, and the eluent is combined to evaporate the solvent to obtain the pure product. The material was...

Embodiment 2

[0033]

[0034] 0.01 mmol cuprous chloride (1 mg), 0.02 mmol 1,3-bis(2,4,6-trimethylphenyl) imidazolium chloride (6.9 mg), 0.2 mmol potassium tert-butoxide (22.4 mg) Put it into a Schlenk reaction tube, vacuumize it, and replace the nitrogen three times, add 1ml of ethanol as a solvent, and stir at room temperature for 15 minutes. Then 0.2 mmol of diphenylacetylene (35.6 mg) and 0.24 mmol of pinacol diborate (61 mg) were dissolved in 2 mL of ethanol, and then added dropwise into the reaction tube, and stirred at room temperature for 5 hours. After the reaction was finished, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure. The mixture of esters is used as the eluent for elution, and the elution process is tracked by TLC, the eluent containing the target product is collected, and the eluent is combined to evaporate the solvent to obtain the pure product. The material was a colo...

Embodiment 3

[0037]

[0038] Add 0.005mmol cuprous chloride (0.5mg), 0.01mmol 1,3-bis(2,4,6-trimethylphenyl) imidazolium chloride (3.4mg), 0.2mmol potassium tert-butoxide (22.4mg ) into the Schlenk reaction tube, evacuated, and filled with nitrogen for 3 times, added 1ml of ethanol as a solvent, and stirred at room temperature for 15 min. Then 0.2mmol of diphenylacetylene (35.6mg) and 0.24mmol of pinacol diborate (61mg) were dissolved in 2mL of ethanol, and added dropwise to the reaction tube, and stirred at room temperature for 5 hours. After the reaction was finished, 100-200 mesh column chromatography silica gel was added to the obtained reaction solution and the solvent was distilled off under reduced pressure. The mixture of esters is used as the eluent for elution, TLC tracks the elution process, collects the eluent containing the target product, combines the eluents and evaporates the solvent to obtain a pure product. The material was a colorless liquid, 55% yield.

[0039] Cha...

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Abstract

The invention discloses a method for highly selectively reducing an alkyne to a Z-olefin. The method comprises the steps of adding cuprous chloride, a ligand and potassium t-butoxide to a Schlenk reaction tube, conducting vacuumizing, adding an organic solvent A under protective gas conditions, and conducting uniform stirring at room temperature; and then dissolving a diphenylacetylene compound shown in a formula I and bis(pinacolato)diboron in an organic solvent B to obtain a solution, dropwise adding the solution to the reaction tube, conducting stirring for reaction at room temperature for1-12 hours, and conducting post-treatment on an obtained reaction solution to obtain a Z-olefin and derivatives thereof represented by a formula II, wherein the ligand is 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride or 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride. The method takes safe cheap ethanol as a hydrogen source, is mild in reaction conditions, saves energy consumption, and inaddition, has the characteristics of high yield, high selectivity, high substrate universality and easy operation.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing organic compounds, in particular to a method for highly selective reduction of alkynes into Z-type alkenes. (2) Background technology [0002] Olefin compounds are important intermediates in organic synthesis and are widely used in the fields of medicine, pesticides and materials science. They are widely used in chemical engineering for polymerization, metathesis, epoxidation, hydroformylation, hydroamination, etc. In this way, the research on the related synthesis technology of alkenes has broad application prospects. [0003] At present, the most commonly used method for the synthesis of olefins reported at home and abroad is still to use the elimination reaction of the corresponding halogenated hydrocarbons or alcohols. In recent decades, cross-coupling reactions utilizing aryl alkenes have also become an important method for the synthesis of functional group-substituted complex alkenes. Furt...

Claims

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Application Information

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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
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