Method of photo-induced catalytic selective synthesis of Z- and E-olefins

A light-induced and selective technology, applied in the field of pharmaceutical and chemical applications, can solve the problems of unfavorable large-scale industrial production, difficulty in obtaining trans-olefins, expensive ammonia borane, etc., achieve good catalytic effect, facilitate post-processing procedures, The effect of maintaining the catalytic effect

Inactive Publication Date: 2019-09-10
NANTONG UNIVERSITY
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0005] 1) Catalytic reduction method with hydrogen as 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 not conducive to large-scale industrial production.
[0006] 2) Catalytic reduction method using ammonia borane as a hydrogen source: Although this method has been greatly improved relative to hydrogen as a hydrogen source, ammonia borane is expensive, and this method requires pre-prepared metal and ligand complexes, making Its economic cost is relatively high, which is not conducive to industrial production
[0007] 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 and ammonia borane as hydrogenation reagents. High equipment requirements, low safety factor, high environmental pollution pressure caused by post-processing, and high production costs make large-scale production face many difficulties

Method used

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  • Method of photo-induced catalytic selective synthesis of Z- and E-olefins
  • Method of photo-induced catalytic selective synthesis of Z- and E-olefins
  • Method of photo-induced catalytic selective synthesis of Z- and E-olefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Synthesis of (E)-1,2-diphenylethylene:

[0043]

[0044] Add raw material 1a (0.20 mmol), [Ir(dtbbpy)(ppy)2][PF6] (10μmol, 8.4mg), PdCl 2 (0.04 mmol, 7.1 mg), DPPE (0.04 mmol, 15.9 mg), TEOA (0.4 mmol), HCOOH (0.4 mmol) and acetonitrile (1.5 mL), stirred at room temperature under white light for 16 hours in an air atmosphere, added acetic acid Diluted with ester (5 mL), washed with saturated brine (5 mL), dried the organic phase with anhydrous magnesium sulfate, spin-dried and then column chromatographed with (n-hexane) as the eluent to obtain 32 mg of product 2a as a white solid. The rate is 90%. 1 H NMR (400 MHz, CDCl 3 ): 7.49 (d, J =8.0 Hz, 4H), 7.34 (t, J = 8.0 Hz, 4H), 7.26 – 7.22 (m, 2H), 7.09 (s, 2H); 13 CNMR (100 MHz, CDCl 3 ) 137.4, 128.8, 127.7, 126.6.

Embodiment 2

[0046] Synthesis of (E)-1-bromo-4-styrylbenzene:

[0047]

[0048] Add raw material 1b (0.20 mmol), [Ir(dtbbpy)(ppy)2][PF6] (10 μmol, 8.4 mg), PdCl2 (0.04 mmol, 7.1 mg), DPPE (0.04 mmol, 15.9 mg) in the reaction flask in sequence , TEOA (0.4mmol), HCOOH (0.4mmol) and acetonitrile (1.5 mL), in air atmosphere, under white light irradiation, stirred at room temperature for 16 hours, added ethyl acetate (5 mL) to dilute, washed with saturated brine (5 mL), The organic phase was dried with anhydrous magnesium sulfate, spin-dried and then column chromatographed with (n-hexane) as the eluent to obtain 42 mg of product 2b as a white solid with a yield of 81%. 1 H NMR (400 MHz, CDCl 3 ): 7.48 – 7.43(m, 4H), 7.35 – 7.31 (m, 4H), 7.23 (d, J =8.0 Hz, 1H), 7.07 (dd, J = 24.0,12.0 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) 137.1, 136.4, 131.9, 129.6, 128.9, 128.1, 128.1, 127.6, 126.7, 121.5.

Embodiment 3

[0050] Synthesis of (E)-1-chloro-4-styrylbenzene:

[0051]

[0052] Add raw material 1c (0.20 mmol), [Ir(dtbbpy)(ppy)2][PF6] (10 μmol, 8.4 mg), PdCl2 (0.04 mmol, 7.1 mg), DPPE (0.04 mmol, 15.9 mg) in the reaction flask in sequence , TEOA (0.4mmol), HCOOH (0.4mmol) and acetonitrile (1.5 mL), in air atmosphere, under white light irradiation, stirred at room temperature for 16 hours, added ethyl acetate (5 mL) to dilute, washed with saturated brine (5 mL), The organic phase was dried with anhydrous magnesium sulfate, spin-dried and then column chromatographed with (n-hexane) as the eluent to obtain 36 mg of product 2c as a white solid with a yield of 84%. 1 H NMR (400 MHz, 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 (100 MHz, CDCl 3 ) d 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 method of photo-induced catalytic selective synthesis of Z- and E-olefins. According to the method, a disubstituted acetylene compound is used as a starting raw material, a cheap acid is used as a hydrogen source, a phosphine is used as a ligand, a metal palladium M<m>X<n> is used as a catalyst, light is used as an inducing initiator, and cis-olefins and trans-olefins canbe obtained in high yield and high selectivity at room temperature. The method adopts the cheap acid as the hydrogen source and light as the inducing initiator, and the reaction is carried out at room temperature. Compared with a traditional hydrogenation strategy, the method greatly reduces economic costs, has simple steps, convenient operation, good product selectivity and high yield, and is suitable for industrialization production.

Description

technical field [0001] The invention relates to the technical field of pharmaceutical and chemical applications, in particular to a method for selectively synthesizing Z- and E-alkenes by light-induced catalysis. Background technique [0002] Olefin compounds are a class of important chemical intermediates and pharmaceutical intermediates in the pharmaceutical and chemical industry, and widely exist in natural products; in the chemical industry, they can be used for catalytic hydrogenation reactions, electrophilic addition reactions, free radical addition reactions, Polymerization reaction, etc., is an extremely important class of organic synthesis reagents; in the field of medicine, it is an important class of drug intermediates, especially trans-olefins are the most widely used. Therefore, olefinic compounds have high application value. Compared with the traditional method, this method is more green, environmentally friendly and economical. It adopts a clean energy photoi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C5/09C07C15/52C07C17/354C07C25/24C07C15/58
CPCC07C5/09C07C17/354C07C15/52C07C25/24C07C15/58
Inventor 杨锦飞杨会会
Owner NANTONG UNIVERSITY
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