102739-73-1Relevant articles and documents
Robust Buchwald-Hartwig amination enabled by ball-milling
Cao, Qun,Nicholson, William I.,Jones, Andrew C.,Browne, Duncan L.
, p. 1722 - 1726 (2019)
An operationally simple mechanochemical method for the Pd catalysed Buchwald-Hartwig amination of arylhalides with secondary amines has been developed using a Pd PEPPSI catalyst system. The system is demonstrated on 30 substrates and applied in the context of a target synthesis. Furthermore, the performance of the reaction under aerobic conditions has been probed under traditional solution and mechanochemical conditions, the observations are discussed herein.
Buchwald-Hartwig Amination of (Hetero)Aryl Tosylates Using a Well-Defined N-Heterocyclic Carbene/Palladium(II) Precatalyst
Zhang, Yin,Lavigne, Guy,César, Vincent
, p. 7666 - 7673 (2015)
The cross-coupling of aryl tosylates with amines and anilines was achieved by using for the first time a Pd-NHC system based on the popular Pd-PEPPSI precatalyst platform in which the anchoring imidazol-2-ylidene ligand IPr (NMe2)2 incorporates two dimethylamino groups as backbone substituents enhancing both the electronic and steric properties of the carbene. The system optimization and its application scope are disclosed.
Facile catalytic SNAr reaction of nonactivated fluoroarenes with amines using η6-benzene ruthenium(II) complex
Otsuka, Maiko,Yokoyama, Hiroya,Endo, Kohei,Shibata, Takanori
, p. 2601 - 2606 (2010)
Catalytic SNAr reaction of fluoroarenes possessing no electron-withdrawing group(s) with cyclic amines was achieved using a readily accessible Ru catalyst, which was prepared from [Ru(benzene)Cl2] 2, AgOTf, and P(p-FC6H4)3. The coexistence of molecular sieves MS4A realized high conversion and various substituted aryl amines were obtained in good to high yields. Georg Thieme Verlag Stuttgart New York.
Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
Tappen, Jens,Rodstein, Ilja,McGuire, Katie,Gro?johann, Angela,L?ffler, Julian,Scherpf, Thorsten,Gessner, Viktoria H.
supporting information, p. 4281 - 4288 (2020/03/13)
Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3P+?C?(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+?C?(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C?N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C?N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h?1.
Dialkylterphenyl Phosphine-Based Palladium Precatalysts for Efficient Aryl Amination of N-Nucleophiles
Rama, Raquel J.,Maya, Celia,Nicasio, M. Carmen
supporting information, p. 1064 - 1073 (2020/01/25)
A series of 2-aminobiphenyl palladacycles supported by dialkylterphenyl phosphines, PR2Ar′ (R=Me, Et, iPr, Cyp (cyclopentyl), Ar′=ArDipp2, ArXyl2f, Dipp (2,6-C6H3-(2,6-C6H3-(CHMe2)2)2), Xyl=xylyl) have been prepared and structurally characterized. Neutral palladacycles were obtained with less bulky terphenyl phosphines (i.e., Me and Et substituents) whereas the largest phosphines provided cationic palladacycles in which the phosphines adopted a bidentate hemilabile k1-P,η1-Carene coordination mode. The influence of the ligand structure on the catalytic performance of these Pd precatalysts was evaluated in aryl amination reactions. Cationic complexes bearing the phosphines PiPr2ArXyl2 and PCyp2ArXyl2 were the most active of the series. These precatalysts have demonstrated a high versatility and efficiency in the coupling of a variety of nitrogen nucleophiles, including secondary amines, alkyl amines, anilines, and indoles, with electronically deactivated and ortho-substituted aryl chlorides at low catalyst loadings (0.25–0.75 mol % Pd) and without excess ligand.
