Novel green method of synthesizing C-C bond and N heterocycle derivatives through transition metal catalyzed C-H carbenoid coupling reaction

A technology of transition metal catalysis and coupling reaction, which is applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, and bulk chemical production, etc. It can solve the problems of low atom utilization rate, inability to realize industrial production, and pollution Environmental and other issues, to achieve good thermal and chemical stability, improve atomic utilization, and improve the effect of reaction safety

Inactive Publication Date: 2019-02-15
SICHUAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The present invention realizes the N 1 ,N 3 -The aryl C-H coupling reaction catalyzed by a disubstituted imidazole type ionic liquid as a solvent, a diazo compound as a carbene donor, and a transition metal catalyzes the traditional use of diazo compounds to construct C-C bonds, C-heterobonds, carbocycles and In heterocycles, there are problems such as lengthy steps, harsh reaction conditions, low atom utilization, use of toxic organic solvents, environmental pollution, high cost, and inability to realize industrial production. It provides a milder, faster, simpler, and more effective method than existing reports. , The preparation method is environmentally friendly and the reaction system can be recycled, which reduces the production of finished products and avoids environmental pollution, and the by-product is only nitrogen, which greatly improves the utilization rate of atoms and has a good application prospect

Method used

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  • Novel green method of synthesizing C-C bond and N heterocycle derivatives through transition metal catalyzed C-H carbenoid coupling reaction
  • Novel green method of synthesizing C-C bond and N heterocycle derivatives through transition metal catalyzed C-H carbenoid coupling reaction
  • Novel green method of synthesizing C-C bond and N heterocycle derivatives through transition metal catalyzed C-H carbenoid coupling reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Implementation Example 1: Synthesis of Compound 1

[0032]

[0033] (1) Add 2-phenylpyridine (31.0 mg, 0.20 mmol), diethyl malonate diazo (44.7 mg, 0.24 mmol), dichloro(pentamethylcyclopentadiene base) rhodium(III) dimer (3.0 mg, 0.025 mmol), silver acetate (4.8 mg, 0.15 mmol), 1-butyl-3-methylimidazole bistrifluoromethanesulfonic acid imide salt (0.3 mL ), and stirred at room temperature for 2 hours.

[0034] (2) After the reaction was completed, ether was added for extraction (1 mL×5), the ether layer was collected, the solvent was removed under reduced pressure, and the residue was separated by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1, v / v) Purified to obtain 55 mg of the target product as a white solid with a yield of 95%; 1H NMR (400 MHz, DMSO- d 6 ) δ 8.61 (ddd, J = 4.8, 1.6, 0.8 Hz, 1H),7.94 (td, J = 7.6, 2.0 Hz, 1H), 7.61 (dt, J =7.6, 0.8 Hz, 1H), 7.56-7.52 (m,1H), 7.50-7.46 (m, 2H), 7.42-7.37 (m, 2H), 5.16 (s, 1H), 4.1...

Embodiment 2

[0035] Implementation Example 2: Synthesis of Compound 2

[0036]

[0037] (1) Add 3-trifluoromethylpyridine (44.6 mg, 0.20 mmol), diethyl malonate diazo (44.6 mg, 0.24 mmol), dichloro(pentamethylcyclopenta Dienyl) rhodium(III) dimer (3.1 mg, 0.025 mmol), silver acetate (5.0 mg, 0.15 mmol), 1-butyl-3-methylimidazole bistrifluoromethanesulfonate imide salt ( 0.3 mL), stirred at room temperature for 12 hours.

[0038] (2) After the reaction was completed, ether was added for extraction (1 mL×5), the ether layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain a colorless oily liquid with a yield of 81%; 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.64(d, J = 4.4 Hz, 1H), 7.98 (t, J = 7.6 Hz, 1H), 7.89 (d, J = 8.4 Hz, 2H), 7.75(d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.49-7.44 (m, 1H), 5.21 (s,1H), 4.16-4.11 (m, 4H), 1.15 (t, J = 7.2 Hz, 6H); 13 C NMR (100 MHz, DMSO...

Embodiment 3

[0039] Implementation Example 3: Synthesis of Compound 3

[0040]

[0041] (1) In a clean reactor, add 2-(2-thiophene)pyridine (32.2 mg, 0.20 mmol), diethyl malonate diazo (44.7 mg, 0.24 mmol), dichloro(pentamethylcyclo Pentadienyl) rhodium(III) dimer (3.1 mg, 0.025 mmol), silver acetate (5.0 mg, 0.15 mmol), 1-butyl-3-methylimidazole bistriflate (0.3 mL), stirred at room temperature for 24 hours.

[0042] (2) After the reaction was completed, ether was added for extraction (1 mL×5), the ether layer was collected, the solvent was removed under reduced pressure, and the residue was separated and purified by silica gel column chromatography to obtain a yellow oily liquid with a yield of 95%; 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.59(ddd, J = 4.8, 1.6, 0.8 Hz, 1H), 7.88 (td, J = 7.6, 1.6 Hz, 1H), 7.66-7.63(m, 2H), 7.34 (ddd, J = 7.6, 4.8, 1.2 Hz, 1H), 7.10 (d, J = 4.8 Hz, 1H), 5.81(s, 1H), 4.15 (q, J = 7.2 Hz, 4H), 1.17 (t, J = 7.2 Hz, 6H); 13 C NMR (100 MHz, DMSO- ...

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Abstract

The invention relates to a novel green synthesis method of efficiently synthesizing C-C bond and N heterocycle derivatives through a transition metal catalyzed C-H active carbene coupling reaction. The method takes N1,N3-di-substituted imidazole ionic liquid as a solvent and takes a diazonium compound as a carbene donor. Compared with the prior art, the method is safer, simpler, and more convenient, efficient and environmentally friendly; functional group tolerance and a yield are high; the solvent and a catalyst can be recycled; the cost is greatly lowered; a byproduct is only nitrogen; the generation of a large amount of waste is avoided; an atom utilization ratio is increased; pre-activation of a substrate is not required; reaction conditions are mild; the operation difficulty is reduced.

Description

technical field [0001] The present invention relates to a N-based 1 ,N 3 - A new method for the green synthesis of disubstituted imidazole-type ionic liquids as solvents, diazo compounds as carbene donors, and C-H coupling reactions catalyzed by transition metals to efficiently form C-C bonds on aryl heterocycles and N-heterocycle derivatives. Background technique [0002] In the past two decades, C–H activation has achieved rapid development in the field of homogeneous catalysis for chemical synthesis, mainly due to the avoidance of preactivation of starting materials and the greatly reduced formation of by-products. 1-3 . However, due to the high bond energy of the C–H bond, metal mediation is indispensable in the C–H activation reaction. Most metal catalysts are relatively scarce and expensive, such as palladium, ruthenium, rhodium, iridium, etc., which to some extent limits the wider application of C-H activation in the field of organic synthesis 4 . [0003] In ord...

Claims

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Application Information

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IPC IPC(8): C07D213/55C07D409/04C07F9/58C07D403/04C07D249/06C07D217/26C07D237/28C07C245/08
CPCC07C245/08C07D213/55C07D217/26C07D237/28C07D249/06C07D403/04C07D409/04Y02P20/54Y02P20/584
Inventor 吴勇海俐张晨管玫
Owner SICHUAN UNIV
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