- Catalytic carbon-nitrogen bond-forming cross-coupling using N-trimethylsilylamines
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Carbon-nitrogen bond-forming cross-coupling reaction of haloarenes with N-trimethylsilyl (TMS)-substituted secondary and primary arylamines proceeded with the aid of a palladium catalyst and a fluoride activator. Various TMS-N(aryl)2, TMS-NH(aryl), and TMS-N(alkyl)2 reacted to give the corresponding coupled products in high yields. Multi-TMS-amine nucleophiles such as N,N-(TMS)2-aniline and N,N′-Ph2-N,N′-(TMS)2-p-phenylenediamine also participated in this C-N coupling to give multiply C-N coupled products in high yields. The novel C-N cross-coupling reaction was successfully applied to C-N bond-forming polymerization. Relative rates of the cross-coupling of p-bromotoluene with N-TMS-substituted primary and secondary amines showed that N-TMS-diphenylamine reacted faster than N-TMS-N-methylaniline or N-TMS-aniline, and N-TMS-morpholine was the least reactive, indicating that the low basicity of the nitrogen nucleophile is the key for the smooth coupling.
- Minami, Yasunori,Komiyama, Takeshi,Shimizu, Kenta,Hiyama, Tamejiro,Goto, Osamu,Ikehira, Hideyuki
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Read Online
- The heterogeneous catalyst using the same and method of manufacturing hydroxytriarylamine compd. (by machine translation)
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PROBLEM TO BE SOLVED: To provide an industrially-useful heterogeneous catalyst for coupling reaction, and a method for producing a triarylamine compound and/or triarylamine polymer using the heterogeneous catalyst. SOLUTION: The heterogeneous catalyst for coupling reaction includes a carrier, a palladium compound, and tri (tert-butyl) phosphine, and is characterized in that the palladium compound content in weight is 0.03 to 0.2 times the carrier weight in terms of palladium atom and the tri (tert-butyl) phosphine content in mole is 0.6 to 12 times one palladium atom mole in the palladium compound. In addition, the heterogeneous catalyst is used. COPYRIGHT: (C)2013,JPO&INPIT
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Paragraph 0088-0089; 0098
(2016/10/09)
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- Silicon-based CN cross-coupling reaction
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Palladium-catalyzed CN bond-forming cross-coupling reaction of N-trimethylsilylamines with aryl bromides and chlorides is found to proceed in the presence of a fluoride activator in 1,3-dimethyl-2-imidazolidinone (DMI), giving triarylamines in excellent yields. When aryl bromide and bis(silyl)amine were used in this reaction, double CN bondforming products were obtained in high yields. The present reaction was successfully applied to CN bond-forming polymerization.
- Shimizu, Kenta,Minami, Yasunori,Goto, Osamu,Ikehira, Hideyuki,Hiyama, Tamejiro
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supporting information
p. 438 - 440
(2014/04/17)
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