CN106866646B - Novel catalytic direct dehydrogenation coupling method for synthesizing alkane compound containing thiophene structure - Google Patents
Novel catalytic direct dehydrogenation coupling method for synthesizing alkane compound containing thiophene structure Download PDFInfo
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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Abstract
The invention provides a novel catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures. The method adopts a one-pot process, uses metal nickel salt as a catalyst, uses non-functionalized thiophene compounds containing different functional groups and aliphatic amide containing a positioning group as raw materials, uses organic acid as a ligand, uses a high-boiling-point polar solvent, inorganic salt as alkali and silver salt as an oxidant, adds a phase transfer catalyst, and then effectively reacts for 24 hours at 160 ℃ to obtain a target compound, wherein the method has the following main advantages: compared with the existing halogenation or lithium salt functionalization method, the method does not need to perform pre-functionalization on the thiophene compound, thereby greatly reducing intermediate steps, and reducing the raw material cost and the waste generated by the reaction. Meanwhile, the method has the characteristics of atom economy and high efficiency.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of catalytic organic synthesis, and particularly relates to a novel catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures.
[ background of the invention ]
The thiophene structure compound is a substance commonly existing in natural products and medicines with biological activity, and can be directly applied to organic synthesis and material research and development, particularly in the fields of photoelectric materials and pharmacy. However, in the current production process, the cross-coupling reaction of the pre-functionalized thiophene reagents, which are present predominantly in halogenated or lithiated form, with the metalated or halogenated aromatic reagents predominates. Therefore, in the synthesis process, the waste generated by the preparation of raw materials becomes an environmental problem to be solved urgently. Therefore, new preparation methods without pre-functionalization have become a hot area of global research. At the present stage, researchers build novel compounds which cannot be obtained by the traditional method through a novel method of direct dehydrogenation coupling catalyzed by transition metals. However, the reaction between an aromatic hydrocarbon or a heterocyclic compound and a thiophene structural compound, i.e., the formation of a C (sp2) -C (sp2) bond, is widely used at present. Or direct dehydrogenation coupling reaction under the catalysis of noble metals such as palladium, rhodium, ruthenium and the like.
There are many inexpensive metals that have been used in catalytic reactions recently, including copper, iron, nickel, etc., but the selection of a new inexpensive and efficient transition metal catalyst remains a significant challenge. You et al report first the rhodium catalyzed direct dehydrocoupling of an aromatic hydrogen ortho to benzoic acid with thiophene[1]. Also reported are nickel-catalyzed direct dehydrocoupling of aromatic substrates with bidentate ligand-localized functional groups to thiophene structures[2]. Chatani et al report nickel catalyzed hydrocarbon activation, a catalytic system capable of catalyzing the sp of aliphatic alkanes3Reacting hydrogen with iodobenzene to perform aromatization[3]。
Inspired by You and Chatani et al, we designed a nickel metal catalytic system. First, nickel coordinates with N on the anchoring functionality to form nickel divalent. And then oxidizing the nickel intermediate by silver salt to generate a trivalent nickel intermediate. And then through electrophilic aromatic substitution reaction and reduction elimination reaction to generate the final product.
Reference documents:
[1]Qin,X.；Li,X.；Huang,Q.；Liu,H.；Wu,D.；Guo,Q.Lan,J.；Wang,R.；You,J.Angew.Chem.Int.Ed.2015,54,7167.
[2]Cheng,Y.；Wu,Y.；Tan,G.；You,J.Angew.Chem.Int.Ed.2016,55,12275.
[3]Aihara,Y.；Chatani,N.J.Am.Chem.Soc.2014,136,898.
[ summary of the invention ]
The invention aims to provide a novel catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures.
In order to achieve the above purpose, the invention provides the following technical scheme:
a novel catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures is characterized in that metal nickel salt is used as a catalyst, non-functionalized thiophene compounds containing different functional groups and aliphatic amide containing a positioning group are used as raw materials, organic acid is used as a ligand, a high-boiling-point polar solvent, inorganic potassium salt is used as alkali, silver salt is used as an oxidant, a phase transfer catalyst is added, and then the reaction is carried out for 24 hours at 160 ℃ to obtain a target compound.
In the synthesis method, the nickel catalyst is one of nickel bromide, nickel fluoride, nickel acetate, nickel chloride, nickel acetylacetonate, nickel acetate, nickel trifluoromethanesulfonate and bis (triphenylphosphine) nickel chloride.
In the synthesis method, the thiophene compound is one of thiophene, 2-chlorothiophene, 2-bromothiophene, 2-iodothiophene, 2-methylthiophene, 2-methoxythiophene, 2-acetylthiophene, 2-ethylformate thiophene, 2-phenylthiophene, benzothiophene, 3-methylthiophene, 3-bromothiophene, bithiophene and bithiophene.
In the above synthesis method, the positioning functional group of the aliphatic amide is 8-aminoquinoline.
In the above synthesis method, the aliphatic amide comprises one of N-8-quinolinetripentanamide, 2-methyl-2-phenyl-N-8-quinolinetripentanamide, 2, 2-methyl-3-phenyl-N-8-quinolinetripentanamide, 1-methyl-N-8-quinolinecarboxamide, 2-methyl-2- (naphthyl-2-methyl) -N-8-quinolinebutanamide, 2, 2-phenyl-N-8-quinolinebutanamide, and 2-methyl-2-phenyl-N-8-quinolinebutanamide
In the synthesis method, the ligand is 2,4, 6-trimethyl benzoic acid.
In the synthesis method, the alkali is one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium hydrogen phosphate and potassium dihydrogen phosphate.
In the above synthesis method, the solvent is one of DMF and DMSO.
In the synthesis method, the silver salt is one of silver carbonate, silver nitrate, silver chloride, silver bromide, silver fluoride, silver oxide, silver acetate and silver trifluoromethanesulfonate.
In the synthesis method, the phase transfer catalyst is one of tetrabutylammonium iodide, tetrabutylammonium bromide and tetracyclohexylammonium iodide.
In the above synthesis method, the catalytic reaction conditions are as follows: the reaction was carried out at 160 ℃ for 24 hours.
[ description of the drawings ]
FIG. 1 shows a schematic diagram of catalytic dehydrogenation coupling reaction and the obtained alkane compound containing thiophene structure.
[ detailed description ] embodiments
The invention provides a novel catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures, which is characterized in that metal nickel salt is used as a catalyst, non-functionalized thiophene compounds containing different functional groups and aliphatic amide containing a positioning group are used as raw materials, organic acid is used as a ligand, a high-boiling-point polar solvent, inorganic potassium salt is used as alkali, silver salt is used as an oxidant, a phase transfer catalyst is added, and then the reaction is carried out for 24 hours at 160 ℃ to obtain a target compound.
The invention is further illustrated below with reference to specific preparation examples:
preparation example 1
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium bromide (0.6mmol), DMSO (0.5mL) under nitrogen, and reacted at 160 ℃ for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 64%.
Preparation example 2
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-chlorothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 63%.
Preparation example 3
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-bromothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 61%.
Preparation example 4
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-iodothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 66%.
Preparation example 5
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-methylthiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 70%.
Preparation example 6
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-methoxythiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 47%.
Preparation example 7
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-acetylthiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 41%.
Preparation example 8
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), ethyl-2-carboxylate thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and 160 ℃ were added to the reaction tube and reacted for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 64%.
Preparation example 9
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), benzothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 73%.
Preparation example 10
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2-phenylthiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 62%.
Preparation example 11
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 3-methylthiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 67%.
Preparation example 12
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 3-bromothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 71%.
Preparation example 13
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), bithiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reaction at 160 ℃ for 24h were added to a 10mL reaction tube. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 64%.
Preparation example 14
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), bitriphenylene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 53%.
Preparation example 15
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), 2, 3-dibromothiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol) were added to a 10mL reaction tube, DMF (0.5mL) was added under nitrogen, and reaction was carried out at 160 ℃ for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 61%.
Preparation example 16
N-8-quinolinetripentanamide (0.2mmol), nickel fluoride (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 48%.
Preparation example 17
N-8-quinolinetripentanamide (0.2mmol), nickel acetate (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 52%.
Preparation example 18
N-8-quinolinetripentanamide (0.2mmol), nickel trifluoromethanesulfonate (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 64%.
Preparation example 19
N-8-quinolinetripentanamide (0.2mmol), bis (triphenylphosphine) nickel chloride (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver carbonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and 160 ℃ were added to a reaction tube and reacted for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 40%.
Preparation example 20
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver nitrate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 12%.
Preparation example 21
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver fluoride (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 6%.
Preparation example 22
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver oxide (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 23%.
Preparation example 23
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver acetate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 42%.
Preparation example 24
N-8-quinolinetripentanamide (0.2mmol), nickel bromide (0.04mmol), 2,4, 6-trimethylbenzoic acid (0.08mmol), potassium dihydrogen phosphate (0.4mmol), thiophene (0.6mmol), silver trifluoromethanesulfonate (0.6mmol), tetrabutylammonium iodide (0.6mmol), DMF (0.5mL) under nitrogen were added to a 10mL reaction tube and reacted at 160 ℃ for 24 h. After the reaction is finished, the temperature is reduced to room temperature, 20ml of distilled water is added, ethyl acetate (3x10ml) is used for extraction, anhydrous sodium sulfate is added for drying, and the product is obtained through column chromatography separation, wherein the yield is 18%.
Claims (3)
1. A catalytic direct dehydrogenation coupling method for synthesizing alkane compounds containing thiophene structures is characterized in that metal nickel salt is used as a catalyst, thiophene and N-8-quinoline pivalic amide are used as raw materials, organic acid is used as a ligand, and a high-boiling-point polar solvent is used; the high-boiling-point polar solvent is one of DMF and DMSO, and the inorganic potassium salt is used as alkali, wherein the alkali is one of potassium carbonate, potassium bicarbonate, potassium hydrogen phosphate and potassium dihydrogen phosphate; silver salt is used as an oxidant, a phase transfer catalyst is added, and then the reaction is carried out for 24 hours at 160 ℃ to obtain a target compound, wherein the structural formula of the target compound is as follows:
the ligand is 2,4, 6-trimethyl benzoic acid; the silver salt is silver carbonate; r1And R2Is methyl; r3Is H.
2. The catalytic direct dehydrogenation coupling method according to claim 1, wherein the catalyst is one of nickel bromide, nickel fluoride, nickel acetate, nickel chloride, nickel acetylacetonate, nickel acetate, nickel trifluoromethanesulfonate, and bis (triphenylphosphine) nickel chloride.
3. The catalytic direct dehydrogenation coupling method according to claim 1, wherein the phase transfer catalyst is one of tetrabutylammonium iodide, tetrabutylammonium bromide and tetracyclohexylammonium iodide.
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| Ni(II)-Catalyzed Oxidative Coupling between C(sp2)−H in Benzamides and C(sp3)−H in Toluene Derivatives;Yoshinori Aihara et al.;《J. Am. Chem. Soc.》;20141027;第15509-15512页 * |
| Nickel Catalysis Enables Oxidative C(sp2)–H/C(sp2)–H Cross-Coupling Reactions between Two Heteroarenes;Yangyang Cheng et al.;《Angew. Chem. Int. Ed.》;20161231;第12275-12279页 * |
| Xurong Qin et al..Rhodium(III)-Catalyzed ortho C¢H Heteroarylation of (Hetero)aromatic Carboxylic Acids: A Rapid and Concise Access to p-Conjugated Poly-heterocycles.《Angew. Chem. Int. Ed.》.2015,第7167-7170页. * |
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