Modern Amination Reactions

Abstract

The synthesis of functionalized aromatic and heteroaromatic amines has attracted much interest due to their importance as building blocks for pharmaceuticals, polymers, or materials. In this microreview, new developments involving palladium-, nickel-, and copper-catalyzed amination reactions are discussed. The synthesis of functionalized secondary amines or diarylamines by addition of polyfunctionalized arylmagne-

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

“…[53,54] Palladium-catalyzed amination has rapidly become an important tool in organic synthesis, pharmaceutical and materials science. [55][56][57][58][59][60][61][62][63][64][65][66][67][68][69] Progress in this reaction have been driven largely by the implementation of new classes of ligands. Initial studies made use of tri-otolylphosphine.…”

Synthesis of Heterocycles by Intramolecular Nucleophilic Substitution at an Electron‐Deficient sp2 Nitrogen Atom

“…Indeed, it led to the initial formation of a nucleophilic addition product with a thioureido structure. However, this intermediate reacted with a second equivalent of isothiocyanate followed by cyclodesulfurization to give 3-phenyl-2-phenylimino-2,6,7,8-tetrahydroimidazo [1,2-a] [1,3,5]triazine-4(3H)-thione. [25] To the best of our knowledge, thus far no report has dealt with the electrophilic amination of ambident amido anions by compounds bearing an electron-deficient sp 2 - [27,28] may exhibit antibacterial and antiproliferative activities.…”

“…[1][2][3][4][5][6][7][8][9] In this process an electronegatively substituted nitrogen compound serves as the electrophilic [NH 2 + ] equivalent (a 1 synthon) for the reaction with carbon, nitrogen, oxygen, sulfur or phosphorus nucleophiles. [10][11][12][13][14][15][16][17] Although there are many synthetic methods reported in the literature for the formation of [R 2 N + ] synthons susceptible to nucleophilic attack, examples of intramolecular electrophilic amination reactions are rare.…”

Copper‐Catalyzed N‐Arylation of Hindered Substrates Under Mild Conditions

“…Successful C À N coupling methods [1] have employed palladium, nickel [2] and copper [3] catalysts in the coupling of amines with aryl halides; however, mild methods are scarce. These reactions typically require stoichiometric quantities of base and elevated reaction temperatures.…”