title: Mechanism of arylboronic acid-catalyzed amidation reaction between carboxylic acids and amines.
abstract: Arylboronic acids were found to be efficient catalysts for the amidation reactions between carboxylic acids and amines. Theoretical calculations have been carried out to investigate the mechanism of this catalytic process. It is found that the formation of the acyloxyboronic acid intermediates from the carboxylic acid and the arylboronic acid is kinetically facile but thermodynamically unfavorable. Removal of water (as experimentally accomplished by using molecular sieves) is therefore essential for overall transformation. Subsequently C-N bond formation between the acyloxyboronic acid intermediates and the amine occurs readily to generate the desired amide product. The cleavage of the C-O bond of the tetracoordinate acyl boronate intermediates is the rate-determining step in this process. Our analysis indicates that the mono(acyloxy)boronic acid is the key intermediate. The high catalytic activity of ortho-iodophenylboronic acid is attributed to the steric effect as well as the orbital interaction between the iodine atom and the boron atom.
authors: College of Chemistry & Chemical Engineering, Shaoxing University, Shaoxing, 312000, China.
authors: Chen
authors: C
authors: Wang
authors: Hai-Zhu
authors: HZ
authors: Yu
authors: Yao
authors: Y
authors: Fu
authors: Qing-Xiang
authors: QX
authors: Guo
mesh_terms: D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D000577:Amides; D000588:Amines; D001897:Boronic Acids; D002264:Carboxylic Acids