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Photo-induced catalytic method for selectively synthesizing cis olefin and trans olefin by using alcohol as hydrogen source

A light-induced and selective technology, which is applied in the field of pharmaceutical and chemical applications, can solve the problems that it is difficult to realize the selective synthesis of cis- and trans-alkenes at the same time, it is unfavorable for large-scale industrial production, and it is difficult to obtain trans-alkenes. Catalytic effect, convenient post-treatment process, low catalyst consumption

Inactive Publication Date: 2019-09-20
NANTONG UNIVERSITY
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  • Summary
  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0005] 1) Catalytic reduction method in which hydrogen is the hydrogen source: This method requires the use of flammable and explosive hydrogen as a hydrogenation reagent, which reduces the safety of the reaction, and it is difficult to obtain trans-olefins due to the cis-addition of hydrogen; in addition, The method is complicated to operate, requires high equipment, and has high economic costs, which is unfavorable for large-scale industrial production;
[0006] 2) Ammoniaborane is the catalytic reduction method of the hydrogen source: although this method has been greatly improved relative to hydrogen as the hydrogen source, the ammonia borane is expensive, and the method needs to prepare the complex of the metal and the ligand in advance, so that Its economic cost is relatively high, which is not conducive to industrial production;
[0007] 3) Catalytic reduction method using acid as a hydrogen source: This method uses acid as a hydrogen source. Although the economic cost has been reduced compared with the previous two strategies, due to the high corrosiveness of acid, it is easy to cause equipment corrosion, which is also not conducive to large-scale industrial production
In addition, this strategy is difficult to simultaneously achieve the selective synthesis of cis- and trans-alkenes
[0008] In summary, substituted olefin compounds have high application value in the pharmaceutical industry and chemical industry, but most of the existing synthetic methods use flammable, explosive and expensive reagents such as hydrogen, ammonia borane, and acid as hydrogenation reagents. , high requirements on equipment, low safety factor, high environmental pollution pressure caused by post-processing, and high production costs, making large-scale production face many difficulties

Method used

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  • Photo-induced catalytic method for selectively synthesizing cis olefin and trans olefin by using alcohol as hydrogen source
  • Photo-induced catalytic method for selectively synthesizing cis olefin and trans olefin by using alcohol as hydrogen source
  • Photo-induced catalytic method for selectively synthesizing cis olefin and trans olefin by using alcohol as hydrogen source

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Synthesis of (E)-1,2-Diphenylethylene:

[0049]

[0050] Add raw material 1a (0.20mmol), Ir(ppy) into the reaction flask 3 (10μmol, 8.4 mg), PdCl 2 (0.04mmol, 7.1mg), DPPE (0.04mmol, 15.9mg), TEOA (0.4mmol), EtOH (0.4mmol) and acetonitrile (1.5mL), in an air atmosphere, stirring at room temperature under white light irradiation for 16 hours, adding ethyl acetate Ester (5mL) was diluted, washed with saturated brine (5mL), the organic phase was dried with anhydrous magnesium sulfate, spin-dried and column chromatography, the eluent was (n-hexane), product 2a was obtained as a white solid 32mg, yield 90 %. 1 H NMR(400MHz, CDCl 3 ): 7.49(d,J=8.0Hz,4H), 7.34(t, J=8.0Hz,4H), 7.26–7.22(m,2H), 7.09(s,2H); 13 C NMR(100MHz, CDCl 3 ) 137.4, 128.8, 127.7, 126.6.

Embodiment 2

[0052] (E) Synthesis of 1-bromo-4-styrylbenzene:

[0053]

[0054] Add raw material 1b (0.20mmol), Ir(ppy) into the reaction flask 3 (10μmol, 8.4 mg), PdCl2 (0.04mmol, 7.1mg), DPPE (0.04mmol, 15.9mg), TEOA (0.4mmol), EtOH (0.4mmol) and acetonitrile (1.5mL), in an air atmosphere, white light irradiation Stir at room temperature for 16 hours and add ethyl acetate (5mL) to dilute, wash with saturated brine (5mL), dry the organic phase with anhydrous magnesium sulfate, spin dry and column chromatography. The eluent is (n-hexane) to obtain product 2b It is a white solid 42 mg, and the yield is 81%. 1 H NMR(400MHz, CDCl 3 ): 7.48–7.43(m,4H), 7.35–7.31 (m,4H), 7.23(d,J=8.0Hz,1H), 7.07(dd,J=24.0,12.0Hz,2H); 13 C NMR(100MHz, CDCl 3 ) 137.1, 136.4, 131.9, 129.6, 128.9, 128.1, 128.1, 127.6, 126.7, 121.5.

Embodiment 3

[0056] (E) Synthesis of 1-chloro-4-styrylbenzene:

[0057]

[0058] Add 1c (0.20mmol), Ir(ppy) to the reaction flask 3 (10μmol, 8.4 mg), PdCl2 (0.04mmol, 7.1mg), DPPE (0.04mmol, 15.9mg), TEOA (0.4mmol), EtOH (0.4mmol) and acetonitrile (1.5mL), in an air atmosphere, white light irradiation Stir at room temperature for 16 hours and add ethyl acetate (5mL) to dilute, wash with saturated brine (5mL), dry the organic phase with anhydrous magnesium sulfate, spin dry and column chromatography. The eluent is (n-hexane) to obtain product 2c It is a white solid 36mg, the yield is 84%. 1 H NMR(400MHz, CDCl 3 ): 7.50 (d, J = 8.0 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 7.38-7.25 (m, 5H), 7.07 (dd, J = 20.0, 16.0 Hz, 2H); 13 C NMR(100MHz, CDCl 3 ) 137.1, 136.0, 133.3, 129.5, 129.0, 128.9, 128.0, 127.8, 127.5, 126.7.

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Abstract

The invention discloses a photo-induced catalytic method for selectively synthesizing a cis olefin and a trans olefin by using alcohol as a hydrogen source. According to the method, a di-substituted acetylene compound is used as an initial raw material, the cheap alcohol is used as the hydrogen source, phosphine and an amine compound are used as ligands, metal palladium MmXn is used as a catalyst, light is used as an induction initiator, and the cis olefin and the trans olefin can be obtained with high yields selectively under a room temperature condition. According to the photo-induced catalytic method for selectively synthesizing the cis olefin and the trans olefin by using the alcohol as the hydrogen source, the cheap alcohol is adopted as the hydrogen source, the light is used as the induction initiator, a reaction is carried out under the room temperature condition, compared with a traditional hydrogenation strategy, the photo-induced catalytic method for selectively synthesizing the cis olefin and the trans olefin by using the alcohol as the hydrogen source has the advantages that the economic cost is greatly reduced, steps are simple, operation is convenient, the product selectivity is good, the yields are high, and the photo-induced catalytic method for selectively synthesizing the cis olefin and the trans olefin by using the alcohol as the hydrogen source is suitable for industrial production.

Description

Technical field [0001] The invention relates to the technical field of medical and chemical applications, in particular to a method for selectively synthesizing cis and trans olefins by light-induced catalysis using alcohol as a hydrogen source. Background technique [0002] Olefin compounds are a class of important chemical intermediates and pharmaceutical intermediates in the pharmaceutical and chemical industry, and are widely found in natural products; in the chemical industry, they can be used to catalyze hydrogenation reactions, electrophilic addition reactions, free radical addition reactions, Polymerization reactions are an extremely important class of organic synthesis reagents; in the field of medicine, they are an important class of pharmaceutical intermediates, especially trans-olefins are the most widely used. Therefore, olefin compounds have high application value. Compared with the traditional method, this method is more green, environmentally friendly and economi...

Claims

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Application Information

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IPC IPC(8): C07C15/52C07C5/09C07C25/24C07C17/354C07C15/58
CPCC07B2200/09C07C15/52C07C15/58C07C25/24
Inventor 杨锦飞杨会会孙斐
Owner NANTONG UNIVERSITY
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