Reductive Molybdenum-Catalyzed Direct Amination of Boronic Acids with Nitro Compounds
The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C?N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. Moreover, this general and step-economical synthesis of aromatic secondary amines showcases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.
Suárez-Pantiga, Samuel,Hernández-Ruiz, Raquel,Virumbrales, Cintia,Pedrosa, María R.,Sanz, Roberto
supporting information
p. 2129 - 2133
(2019/01/25)
Nickel-Catalyzed Kumada Coupling of Boc-Activated Aromatic Amines via Nondirected Selective Aryl C-N Bond Cleavage
A nickel-catalyzed Kumada coupling of aniline derivatives was developed by selective cleavage of aryl C-N bonds under mild reaction conditions. Without preinstallation of an ortho directing group on anilines, the cross-coupling reactions of Boc-protected aromatic amines with aryl Grignard reagents afforded unsymmetric biaryls. Mechanistic studies by DFT calculations revealed that the nickel-mediated C-N bond cleavage is the rate-limiting step.
Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines.
Vantourout, Julien C.,Law, Robert P.,Isidro-Llobet, Albert,Atkinson, Stephen J.,Watson, Allan J. B.
p. 3942 - 3950
(2016/05/24)
Zinc-promoted, iridium catalyzed reductive alkylation of primary amines with aliphatic ketones in aqueous medium
The reductive alkylation of primary aromatic and aliphatic amines with aliphatic ketones has been achieved in aqueous acidic medium using commercially available, non-activated zinc dust catalyzed by a very small quantity of iridium bromide. Anilines react well in aqueous formic acid, whereas monoalkylamines require 1,4-dioxane as a co-solvent and sulfuric acid as the proton source. A plausible mechanism via low-valent iridium hydride species is proposed.
da Silva, Renato A.,Bieber, Lothar W.
scheme or table
p. 689 - 691
(2010/04/02)
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