223794-26-1Relevant articles and documents
Buchwald-Hartwig amination of aryl esters and chlorides catalyzed by the dianisole-decorated Pd-NHC complex
Song, A-Xiang,Xiong, Hong-Gang,Xu, Chang,Yao, Hua-Gang,Zheng, Di-Zhong
supporting information, p. 2096 - 2101 (2022/04/01)
A modular and generic method for the Buchwald-Hartwig amination reactions of relatively unreactive aryl esters as acyl electrophiles and aryl chlorides as aryl electrophiles has been developed, leading to the efficient synthesis of amides/amines under air conditions and with low catalyst loadings. The success of this catalytic protocol is mainly attributed to the modification of the Pd-IPr skeleton with sterically hindered and electron-donating anisole groups. This method also features good functional group tolerance and excellent chemoselectivities. In summary, the results presented herein suggest the possibility of developing a versatile and general protocol for diverse electrophiles to undergo the Buchwald-Hartwig amination reactions, avoiding too much consideration of the reaction conditions for the substrate-dependent C-N bond formations.
Arylation of Amines in Alkane Solvents by using Well-Defined Palladium-N-Heterocyclic Carbene Complexes
Marelli, Enrico,Chartoire, Anthony,Le Duc, Gaetan,Nolan, Steven P.
, p. 4021 - 4024 (2015/12/26)
The use of the ITent-based series of Pd-N-heterocyclic carbenes precatalysts (Tent= Tentacular) enables the Buchwald-Hartwig amine arylation reaction in apolar alkane solvents. The use of such solvents is rare because of their poor solvation properties. Nonetheless, they could be of interest for industrial applications, as they can be disposed of in an energetically favorable manner and may potentially simplify product isolation. The excellent solubility of the precatalysts permitted the desired products to be obtained in yields ranging from 75 to 96 %, even with deactivated and functionalized coupling partners. Fueling cross-couplings: The use of ITent-based Pd precatalysts (Tent=tentacular) enables the Buchwald-Hartwig amine arylation reaction in alkane solvents. Such solvents could be of interest for industrial applications, as they can be disposed of in an energetically favorable manner and may potentially simplify product isolation. Yields ranging from 75 to 96 % are obtained, even with challenging substrates.
Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride
Samblanet, Danielle C.,Schmidt, Joseph A. R.
, p. 7 - 18,12 (2012/12/12)
While pursuing the development of new hydroamination catalysts, a 3-iminophosphine palladium(II) chloride complex [(3IP)PdCl2] was synthesized that has subsequently proven to be an effective precatalyst for the aryl amination of bromoarenes. This (3IP)PdCl2 complex has been utilized in the catalytic aryl amination of both bromobenzene and bromopyridine derivatives, specifically yielding excellent activity in coupling reactions involving bromobenzene, 4-bromotoluene, and 2-bromopyridine. Using a standard set of catalytic conditions, many alkyl and aryl amines have been investigated as coupling partners in the aryl amination of bromoarenes. In general, secondary alkyl amines and ortho-substituted anilines proved to be the best substrates for this reaction, commonly giving quantitative conversion to products, while primary amines and other anilines gave only poor to moderate results. Catalytic screening data, product yields, and full characterization of isolated products are included.
