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Method for synthesizing cis-olefin by catalyzing decarboxylation coupling reaction of NHP ester and aryl-terminated alkyne with iridium

An aryl alkyne, decarboxylation coupling technology, applied in organic chemistry methods, chemical instruments and methods, condensation between hydrocarbons and non-hydrocarbons to produce hydrocarbons, etc., to achieve the effects of high yield, simple operation and mild conditions

Inactive Publication Date: 2019-02-01
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The most common method for the synthesis of z-alkenes is the Wittig reaction, but it is non-catalytic and the reaction produces stoichiometric amounts of phosphine oxide waste

Method used

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  • Method for synthesizing cis-olefin by catalyzing decarboxylation coupling reaction of NHP ester and aryl-terminated alkyne with iridium
  • Method for synthesizing cis-olefin by catalyzing decarboxylation coupling reaction of NHP ester and aryl-terminated alkyne with iridium
  • Method for synthesizing cis-olefin by catalyzing decarboxylation coupling reaction of NHP ester and aryl-terminated alkyne with iridium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] Synthesis and separation and purification of 1-(2-cyclohexylvinyl)-benzene:

[0067] Add the corresponding NHP ester (655.8mg, 0.4mmol, 6eq), Ir(ppy) 3 (2.6mg, 0.4mmol, 0.01eq); then add DIPEA (4.8mL; 68.7eq) and DMA (3.2mL) as solvents; degas with Ar balloon for 15min, then add phenylacetylene (44μL, 0.4mmol, 1eq), then seal the reaction bottle with a blue light of 36°C for light reaction for 18 hours; after the reaction is completed, extract the reaction mixture twice with 20mL EA, combine the organic phases and wash with saturated brine, then add anhydrous sodium sulfate to dry After the drying is completed, the organic solvent is spin-dried under reduced pressure to obtain a crude product; the crude product is separated by column separation using analytically pure PE as an eluent to obtain the final product; 1-(2-cyclohexylvinyl)benzene is a colorless oil Liquid, the productive rate is 71%, and wherein the ratio of cis-isomer and trans-isomer is 80:20 (cis-trans ra...

Embodiment 2

[0070] Synthesis, separation and purification of 1-(2-cyclohexylvinyl)-4-methyl carboxylate benzene: Add the corresponding NHP ester (655.8mg, 0.4mmol, 6eq) in sequence to a 10mL glass bottle equipped with a magnetic stirrer, Ir(ppy) 3 (2.6mg, 0.4mmol, 0.01eq); then DIPEA (4.8mL) and DMA (3.2mL) were added as solvents; a balloon filled with Ar was degassed for 15min, and then methyl 4-ethynylbenzoate (64mg, 0.4mmol, 1eq), then seal the reaction vial with a 36° blue light for light reaction for 18 hours; after the completion of the reaction, extract the reaction mixture twice with 20mL EA, combine the organic phases and wash with saturated saline, then add anhydrous Sodium sulfate drying; after drying, the organic solvent was spin-dried under reduced pressure to obtain a crude product; the crude product was separated by column using analytically pure PE as an eluent to obtain the final product as a colorless oily liquid with a yield of 75%. (The ratio of Z / E is 87:13)

[0071...

Embodiment 3

[0073] Synthesis, separation and purification of 1-(2-cyclohexylvinyl)-4-methylbenzene: Add the corresponding NHP ester (655.8mg, 0.4mmol, 6eq), Ir (ppy) 3 (2.6mg, 0.4mmol, 0.01eq); then DIPEA (4.8mL) and DMA (3.2mL) were added as solvents; a balloon filled with Ar was degassed for 15min, and then 4-methylphenylacetylene (50.8μL, 0.4 mmol, 1eq), then the reaction bottle was sealed with a blue light of 36°C for light reaction for 18 hours; after the reaction was completed, the reaction mixture was extracted twice with 20mL EA, the organic phases were combined and washed with saturated brine, and then anhydrous sulfuric acid was added Sodium drying; after drying, the organic solvent was spin-dried under reduced pressure to obtain a crude product; the crude product was separated by column using analytically pure PE as an eluent to obtain the final product as a colorless oily liquid with a yield of 68%. (The ratio of Z / E is 76:24)

[0074] 1 H NMR (400MHz, CDCl 3): δ7.25-7.08(...

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Abstract

The invention provides a method for synthesizing Z-selective olefin by catalyzing a decarboxylation coupling reaction of an NHP ester and aryl-terminated alkyne with iridium. The aryl-terminated alkyne and its derivative and the NHP ester undergo a one-pot reaction under the irradiation of blue lights under the catalysis of iridium to obtain the corresponding Z-selective olefin compound. The method has the advantages of simple process and high cis-selectivity.

Description

technical field [0001] The invention relates to a method for synthesizing Z-selective alkenes by iridium-catalyzed decarboxylation coupling reaction of NHP esters and terminal aryl alkynes. The invention belongs to the field of synthesizing olefin pharmaceutical intermediates. Background technique [0002] Olefins are among the most important organic compounds in the chemical, material and pharmaceutical industries. Although the preparation of e-alkenes is well established, many efficient synthetic methods for olefination have been developed, such as Wittig reaction, Peterson olefination, Julia olefination, Heck reaction, olefin transposition, Negishi-type organometallic reagent addition to alkyl cations and other types of reactions, but the synthesis of z-alkenes is not so straightforward. The most common method for the synthesis of z-alkenes is the Wittig reaction, but it is noncatalytic and the reaction produces stoichiometric amounts of phosphine oxide waste. In recen...

Claims

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Application Information

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IPC IPC(8): C07C15/52C07C2/86C07C69/78C07C67/343C07D213/127C07C15/44C07D307/06C07D207/06C07C271/24C07C269/06
CPCC07B2200/09C07C15/44C07C15/52C07C69/78C07C271/24C07C2601/04C07C2601/14C07D207/06C07D213/127C07D307/06Y02P20/55
Inventor 唐真宇代国丽赖淑珍
Owner CENT SOUTH UNIV
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