We report herein Cu-catalyzed aerobic oxygenation of aliphatic C-H bonds with hydroperoxides, which proceeds by 1,5-H radical shift of putative oxygen-centered radicals (O-radicals) derived from hydroperoxides followed by trapping of the resulting carbon-centered radicals with molecular oxygen.

The mutagenicity of 17 aliphatic epoxides was determined using the specially constructed mutants of Salmonella typhimurium developed by Ames. The activity of these epoxides together with those reported in the literature as mutagens in strains TA100 and TA1535 depended on the degree of substitution around the oxirane ring. Monosubstituted oxiranes were the most potent mutagens in both strains. 1...

Cobalt-catalysed sp(2) C-H bond functionalization has attracted considerable attention in recent years because of the low cost of cobalt complexes and interesting modes of action in the process. In comparison, much less efforts have been devoted to the sp(3) carbons. Here we report the cobalt-catalysed site-selective dehydrogenative cyclization of aliphatic amides via a C-H bond functionalizati...

Aldoxime dehydratase is a heme-containing enzyme that utilizes the ferrous rather than the ferric ion to catalyze the synthesis of nitriles by dehydration of the substrate. We report a theoretical study of this enzyme aimed at elucidating its catalytic mechanism and understanding this oxidation state preference (Fe(2+) versus Fe(3+)). The uncatalyzed dehydration reaction was modeled by includin...

In the mononuclear title compound, [Ni(CH(3)COO)(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom is coordinated by two pyridine-2-aldoxime (PaoH) ligands and two acetate groups, with cis coordination for the pairs of identical ligands. While each acetate group binds to the Ni(II) atom by one O atom, each PaoH chelates the Ni(II) atom through two N atoms. The O atom on PaoH is not deprotonated and does n...