N‐(1‐Oxy‐2‐picolyl)oxalamic Acid as an Efficient Ligand for Copper‐Catalyzed Amination of Aryl Iodides at Room Temperature

Abstract

N‐(1‐Oxy‐pyridin‐2‐ylmethyl)oxalamic acid was identified as efficient ligand for CuI‐catalyzed amination of aryl halides at room temperature. In our catalytic system, N‐arylation of cyclic secondary amines, primary amines, amino acids, and ammonia proceeded with moderate to excellent yields and high functional group tolerance.

Recent Advances and Perspectives in the Copper‐Catalysed Amination of Aryl and Heteroaryl Halides

“…Copper‐catalysed amination of haloarenes involving an active ligand was developed using 10 mol % CuI, 20 mol % N ‐(1‐Oxy‐2‐picolyl)oxalmic acid and 2 mmol K 3 PO 4 in 1 mL DMSO/H 2 O (10:1) at 20–80 °C ( Scheme ) . Both electron‐deficient and electron‐rich aryl iodides afforded excellent yields of the products while aryl bromides with electron‐deficient moieties afforded the respective products in good yield.…”

Mechanism of the Ullmann Biaryl Ether Synthesis Catalyzed by Complexes of Anionic Ligands: Evidence for the Reaction of Iodoarenes with Ligated Anionic CuI Intermediates

“…3a,4 Ancillary ligands used for this chemistry have included phenanthrolines, 5 bipyridines, 6 dia-mines, 7 dipyridylimines, 8 amino acids, 9 8-hydroxyquinolines, 10 diketones, 11 pyridylketones, 12 and others. 13 These widely used ancillary ligands typically fall into two structural types: neutral, bidentate ancillary ligands (LL), such as phenanthrolines and bipyridines, and anionic, bidentate ancillary ligands [H(LX)], such as 8-hydroxyquinolines and diketones.…”

Microcrystalline solid–solid transformations of conformationally-responsive solvates, desolvates and a salt of N,N′-(1,4-phenylene)dioxalamic acid: the energetics of hydrogen bonding and n/π → π* interactions

“…16 The chemistry of the H 2 pOx ligand for metallic complexes and magnetochemistry have been summarized elsewhere. [17][18][19] In the context of biological activity, Cu(II) oxalamic acid complexes have been found active against Gram-positive bacteria. 20 Oxalamic acid derivatives are flat due to the formation of intramolecular hydrogen bonds between the amide NH and the COOH carbonyl oxygen atom.…”