Efficient Iron/Copper Co‐Catalyzed Arylation of Nitrogen Nucleophiles

Abstract

An ideal pair: Various substituted aryl halides react under mild conditions with nitrogen heterocycles in the presence of catalytic amounts of [Fe(acac)3] (acac=acetylacetonate) and copper salts to give the corresponding cross‐coupling products in high yields (see scheme). This cheap and environmentally friendly co‐catalyst system is the first example of cooperative Fe/Cu catalysis in this type of NC bond formation.

A General Ruthenium‐Catalyzed Synthesis of Aromatic Amines

“…2-octylamine, cyclohexylamine, and cyclooctylamine gave yields of isolated product of 99 % (Table 4, entries [4][5][6]. Moreover, furane-, thiophene-, and indole-substituted amines gave yields up to 97 % (Table 4, entries 7-9).…”

“…Among the various methods, the widely used palladium-and copper-catalyzed aminations of aryl halides, tosylates, and triflates are probably most important. [5,6] In comparison to these substrates, anilines are readily available and inexpensive. In principle, aryl amines could be aminated, leaving ammonia as the only by-product (Scheme 1).…”

A Series of Novel N,N‐Donor Ligands with Binaphthyl Backbones

“…A second copper-based catalyst system -[CuO/Fe(acac) 3 /Cs 2 CO 3 ] -with DMF or NMP as the solvent, recently reported by Taillefer et al, [23] led to slightly better yields: with 2,2Ј-dibromo-1,1Ј-binaphthyl about a 25 % yield of the desired ligand 1 was obtained after 48 h at 160°C. The yield is poorer and the reaction time much longer than for the published synthesis of 1-(2-naphthyl)pyrazole, probably due to the steric demand of the bulky 1,1Ј-binaphthyl moiety.…”

A New, Efficient and Recyclable Lanthanum(III) Oxide‐ Catalyzed CN Cross‐Coupling

“…Taillefer et al reported the N-arylation process by iron-copper combined catalysis. [11] Very recently, ironcatalyzed N-arylation of various nitrogen nucleophiles has been reported. [12] For a long time, there have been numerous methods developed involving various metal salts such as Pd, [13] Cu, [14] Ni, [15] Cd, [16] to synthesize N-arylated motifs.…”