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Method for catalytic-selectively synthesizing Z- and E-alkene through alcohol supply hydrogen iridium controlled by ligand

A selective and ligand-based technology, applied in chemical instruments and methods, hydrogenation to hydrocarbons, organic chemistry, etc., can solve the problem that it is difficult to realize the selective synthesis of Z- and E-olefins at the same time, which is unfavorable for large-scale industrial production and difficult to achieve. The problem of obtaining trans olefins, etc., achieves the effects of good catalytic effect, convenient post-processing procedures, and wide source of raw materials

Active Publication Date: 2019-01-04
NANTONG UNIVERSITY
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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 not conducive to large-scale industrial production; 2) the catalytic reduction method of 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 the method needs to pre-prepare the complex of metal and ligand, so that its economic cost is higher, which is not conducive to industrial production; 3) acid is the catalytic reduction method of hydrogen source: this method uses acid as hydrogen source , although the economic cost has been reduced compared with the first two strategies, but due to the high corrosiveness of acid, it is easy to cause corrosion of equipment, which is also not conducive to large-scale industrial production
In addition, this strategy is difficult to simultaneously achieve the selective synthesis of Z- and E-alkenes
[0006] In summary, quinoline compounds have high application value in the pharmaceutical industry and chemical industry, but the existing synthetic methods need to use flammable, explosive, corrosive or expensive substances such as hydrogen, acid and ammonia borane. As a hydrogenation reagent, the reagent has high requirements on equipment, low safety factor, high environmental pollution pressure caused by post-processing, and high production cost, which makes large-scale production face many difficulties

Method used

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  • Method for catalytic-selectively synthesizing Z- and E-alkene through alcohol supply hydrogen iridium controlled by ligand
  • Method for catalytic-selectively synthesizing Z- and E-alkene through alcohol supply hydrogen iridium controlled by ligand
  • Method for catalytic-selectively synthesizing Z- and E-alkene through alcohol supply hydrogen iridium controlled by ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0043]

[0044] Add raw material 1a (0.20mmol) and EtOH (4mmol, 232L) successively in reaction flask, [Ir(cod)Cl] 2 (10μmol, 8.4mg), DPPE (0.04mmol, 15.9mg) and tetrahydrofuran (1.5mL), in a nitrogen atmosphere, stirred at 120°C for 22 hours, cooled to room temperature, diluted with ethyl acetate (5mL), saturated saline (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 33 mg of product 2a as a white solid, with a yield of 92%. 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

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

[0047]

[0048] Add raw material 1b (0.20mmol) and EtOH (4mmol, 232L) successively in reaction flask, [Ir(cod)Cl] 2 (10μmol, 8.4mg), DPPE (0.04mmol, 15.9mg) and tetrahydrofuran (1.5mL), in a nitrogen atmosphere, stirred at 120°C for 22 hours, cooled to room temperature, diluted with ethyl acetate (5mL), saturated saline (5 mL), the organic phase was dried with anhydrous magnesium sulfate, spin-dried and then column chromatographed, the eluent was (n-hexane), and the product 2b was obtained as 44 mg of a white solid, with a yield of 85%. 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

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

[0051]

[0052] Add raw material 1c (0.20mmol) and EtOH (4mmol, 232L) successively in reaction flask, [Ir(cod)Cl] 2 (10μmol, 8.4mg), DPPE (0.04mmol, 15.9mg) and tetrahydrofuran (1.5mL), in a nitrogen atmosphere, stirred at 120°C for 22 hours, cooled to room temperature, diluted with ethyl acetate (5mL), saturated saline (5 mL), the organic phase was dried with anhydrous magnesium sulfate, spin-dried and then column chromatographed, the eluent was (n-hexane), and the product 2c was obtained as 36 mg of a white solid, with a yield of 84%. 1 H NMR (400MHz, CDCl 3 ):7.50(d, J=8.0Hz, 2H), 7.44(d, J=8.0Hz, 2H), 7.38-7.25(m, 5H), 7.07(dd, J=20.0, 16.0Hz, 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 method for catalytic-selectively synthesizing Z- and E-alkene through alcohol supply hydrogen iridium controlled by a ligand. The method comprises the following steps: usinga disubstituted acetylene compound as a starting raw material, using cheap alcohol as a hydrogen source, and using a metal iridium catalyst MmXn for catalyzing, under the control of a phosphine ligandand a diene ligand, to obtain cis-alkene and trans-alkene in high yield and high selectivity. The method is capable of using the cheap alcohol as the hydrogen source. Compared with a traditional hydrogenation strategy, economic cost is greatly reduced, and the process is simple. A metal iridium complex catalyst does not need to be prepared in advance. The operation is convenient, the product selectivity is good, the yield is high, and the method is suitable for industrial 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 ligand-regulated alcohol hydrogen-donating iridium 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. Through this method, not only can use cheap alcohol as a hydrogen source to synthesize Z-alkenes and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B35/02C07C5/09C07C15/52C07C17/354C07C25/24
CPCC07B35/02C07C5/09C07C17/354C07C15/52C07C25/24
Inventor 杨锦飞孙斐王成牛
Owner NANTONG UNIVERSITY
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