255835-94-0Relevant articles and documents
Visible-Light-Enabled Direct Decarboxylative N-Alkylation
Arman, Hadi D.,Dang, Hang T.,Haug, Graham C.,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Vuong, Ngan T. H.
supporting information, p. 7921 - 7927 (2020/04/10)
The development of efficient and selective C?N bond-forming reactions from abundant feedstock chemicals remains a central theme in organic chemistry owing to the key roles of amines in synthesis, drug discovery, and materials science. Herein, we present a dual catalytic system for the N-alkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids, by-passing their preactivation as redox-active esters. The reaction, which is enabled by visible-light-driven, acridine-catalyzed decarboxylation, provides access to N-alkylated secondary and tertiary anilines and N-heterocycles. Additional examples, including double alkylation, the installation of metabolically robust deuterated methyl groups, and tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation (DDA) reaction.
A Highly Selective Palladium-Catalyzed Aerobic Oxidative Aniline-Aniline Cross-Coupling Reaction
Matsumoto, Kenji,Takeda, Satoshi,Hirokane, Tsukasa,Yoshida, Masahiro
supporting information, p. 7279 - 7283 (2019/09/30)
The first catalytic oxidative aniline-aniline cross-coupling reaction using oxygen as the terminal oxidant is reported. Anilines possessing a pyrrolidino group can be preferentially oxidized under mild aerobic conditions and reacted with other anilines to afford a variety of nonsymmetrical 2-aminobiphenyls with high selectivities. A heterogeneous palladium catalyst is used for the dehydrogenative cross-coupling of anilines with structurally diverse arenes. This reaction does not require stoichiometric oxidants and is an economical and environmentally friendly method.
Simple, efficient catalyst system for the palladium-catalyzed amination of aryl chlorides, bromides, and triflates
Wolfe, John P.,Tomori, Hiroshi,Sadighi, Joseph P.,Yin, Jingjun,Buchwald, Stephen L.
, p. 1158 - 1174 (2007/10/03)
Palladium complexes supported by (o-biphenyl)P(t-Bu)2 (3) or (o- biphenyl)PCy2 (4) are efficient catalysts for the catalytic amination of a wide variety of aryl halides and triflates. Use of ligand 3 allows for the room-temperature catalytic amination of many aryl chloride, bromide, and triflate substrates, while ligand 4 is effective for the amination of functionalized substrates or reactions of acyclic secondary amines. The catalysts perform well for a large number of different substrate combinations at 80-110 °C, including chloropyridines and functionalized aryl halides and triflates using 0.5-1.0 mol % Pd; some reactions proceed efficiently at low catalyst levels (0.05 mol % Pd). These ligands are effective for almost all substrate combinations that have been previously reported with various other ligands, and they represent the most generally effective catalyst system reported to date. Ligands 3 and 4 are air-stable, crystalline solids that are commercially available. Their effectiveness is believed to be due to a combination of steric and electronic properties that promote oxidative addition, Pd-N bond formation, and reductive elimination.