85895-80-3Relevant articles and documents
Nickel-Catalyzed C-N Cross-Coupling of Ammonia, (Hetero)anilines, and Indoles with Activated (Hetero)aryl Chlorides Enabled by Ligand Design
McGuire, Ryan T.,Paffile, Julia F. J.,Zhou, Yuqiao,Stradiotto, Mark
, p. 9292 - 9297 (2019/10/11)
The Ni(II) precatalyst (C1) featuring the phosphonite ancillary ligand Phen-DalPhos (L1) was employed in the cross-coupling of (hetero)anilines with (hetero)aryl chlorides and in the diarylation of ammonia with (hetero)aryl chlorides to afford heteroatom-dense di(hetero)arylamines. The PAd2-DalPhos precatalyst C4 provided complementary reactivity in cross-couplings of indoles with (hetero)aryl chlorides. Taken together, the demonstration of room-temperature reactivity within each of the reaction classes examined and the observation of useful chemoselectivity at low loading (≤0.5 mol % Ni) and on gram-scale distinguishes C1 and C4 from other metal catalysts (i.e., copper, palladium, nickel, or other) within the field of C-N cross-coupling chemistry.
The synthesis and application of novel Ni(ii) N-alkyl dipyridylaldiminato complexes as selective ethylene oligomerisation catalysts
Swarts, Andrew J.,Mapolie, Selwyn F.
, p. 9892 - 9900 (2014/06/24)
A series of N-alkyl 2,2′-dipyridylamine ligands of general formula (2-C5H3NR)2NR′, (a): R = H, R′ = Me; (b): R = H, R′ = benzyl; (c): R = H, R′ = methylcyclohexyl; (d): R = H, R′ = neopentyl; (e): R = Me, R′ = Me) were prepared by a modified method involving base-mediated N-alkylation with the respective alkyl halide. Reaction of the ligands, a-e, with NiCl2(DME) allowed for the isolation of μ-Cl Ni(ii) complexes: [Ni(μ-Cl){a}Cl]2 (1a); [Ni(μ-Cl){b}Cl]2 (1b); [Ni(μ-Cl){c}Cl]2 (1c); [Ni(μ-Cl){d}Cl]2 (1d) and [Ni(μ-Cl){e}Cl]2 (1e). The complexes were characterised by FT-IR spectroscopy, magnetic susceptibility measurements, mass spectrometry, elemental analyses and in the case of 1a, SCD analysis. In the case of complex 1e, an acid-mediated hydrolysis process was identified. The product of hydrolysis, the protonated ligand and a tetrachloronickelate salt (1e-A), was characterised by SCD analysis. Activation of 1a-1e with alkyl aluminium reagents generated highly active catalysts for the oligomerisation of ethylene, with activities of up to 864 kg oligomers molNi-1 h-1 and high selectivity toward the formation of butenes. In general, trans 2-butene was observed as the major isomer, with the exception of 1e. In the case of 1e, the selectivity for 1-butene was 98%, thereby demonstrating the significant effect that the introduction of a low degree of steric pressure in the coordination sphere of the catalyst has on selectivity.
Selective one-pot synthesis of symmetrical and unsymmetrical di- and triarylamines with a ligandless copper catalytic system
Tlili, Anis,Monnier, Florian,Taillefer, Marc
supporting information; experimental part, p. 6408 - 6410 (2012/07/27)
The one-pot synthesis of symmetrical or unsymmetrical di- or triarylamines using aryl iodides or bromides and LiNH2 as ammonia source is reported. This highly selective method is based, for the first time, on a copper-catalyzed system, which does not require the presence of any additional ligand.
