14162-88-0Relevant articles and documents
A tautomeric ligand enables directed C-H hydroxylation with molecular oxygen
Li, Zhen,Wang, Zhen,Chekshin, Nikita,Qian, Shaoqun,Qiao, Jennifer X.,Cheng, Peter T.,Yeung, Kap-Sun,Ewing, William R.,Yu, Jin-Quan
, p. 1452 - 1457 (2021/06/30)
Hydroxylation of aryl carbon-hydrogen bonds with transition metal catalysts has proven challenging when oxygen is used as the oxidant. Here, we report a palladium complex bearing a bidentate pyridine/ pyridone ligand that efficiently catalyzes this reaction at ring positions adjacent to carboxylic acids. Infrared, x-ray, and computational analysis support a possible role of ligand tautomerization from monoanionic (L,X) to neutral (L,L) coordination in the catalytic cycle of aerobic carbon-hydrogen hydroxylation reaction. The conventional site selectivity dictated by heterocycles is overturned by this catalyst, thus allowing late-stage modification of compounds of pharmaceutical interest at previously inaccessible sites.
Oxidation of 3-hydroxy-6-methyl-2-pyridinemethanol by chromium(VI) in acidic aqueous media; kinetic and EPR studies
Kita,Wrzeszcz
, p. 355 - 364 (2007/10/03)
Kinetics of oxidation of 3-hydroxy-6-methyl-2-pyridinemethanol (hmpol) by CrVI at HClO4 was studied under the pseudo-first-order conditions. The hmpol oxidation products were the appropriate aldehyde (hmpal) and acid (hmpac) coordinated to the chromium(III). The linear dependence of the pseudo-first-order rate constant (kobs) on [hmpol] at 1.0 and 2.0 M HClO4 and a parabolic dependence of kobs on [H+] were established. The apparent activation parameters were determined from the second-order rate constants at 1.0 M HClO4. The presence of the CrII and CrIV intermediates was deduced, based on rate retardation effect caused by O2 and MnII respectively, whereas the presence of CrV was established by EPR. Some correlations between the structure and stability of intermediate chromium(V) complexes have been discussed from EPR spectra, recorded during the redox process.