Here we report a detailed theoretical study of the mechanism of Cu+-catalyzed domino rearrangement of 2-methyl-N-methoxyaniline with a deep understanding of the unique motivation and selectivity of these migrations. We find that the Cu+ catalyst accelerates the [1,3]-methoxy migration to the methyl-bound ortho position of umpolung phenyl. The following domino transfer prefers methyl [1,2]-migration, and the rate-determining step for the whole reaction is the transfer of a proton from the phenyl ring to amine to finish the catalytic cycle.

Two new water-soluble metal carboxyl porphyrins, manganese (III) meso-tetrakis (carboxyl) porphyrin and iron (III) meso-tetrakis (carboxyl) porphyrin, were synthesized and characterized. Their interactions with ct-DNA were investigated by UV-Vis titration, fluorescence spectra, viscosity measurement and CD spectra. The results showed they can strongly bind to ct-DNA via outside binding mode. Electrophoresis experiments revealed that both complexes can cleave pBR322 DNA efficiently in the presence of hydrogen peroxide, albeit 2-Mn exhibited a little higher efficiency. The inhibitor tests suggest the oxidative DNA cleavage by these two complexes may involve hydroxyl radical active intermediates. Notably, 2-Mn exhibited considerable photocytotoxicity against Hep G2 cell via triggering a significant generation of ROS and causing disruption of MMP after irradiation.

A practical and straightforward methodology toward the synthesis of non-fused N-aryl azepane derivatives with diversity is described. These Pd/LA-catalyzed reactions proceed smoothly under extremely mild conditions with ample reaction scope...

A theoretical investigation on Mobius and Wagner-Meerwein rearrangements of 2-methyl-N-methoxyaniline catalyzed by NHCÀ Ag(I)/Au(I) catalysis is presented in this work, which reveals that the reaction mechanism depends on the oxidative state tendency of the metal center. The calculated results show that Ag + /Au + catalyzed rearrangements of 2methyl-N-methoxyaniline undergo three main steps: the cleavage of the NÀ O bond via oxidative addition, stepwise methoxy Mobius rearrangements, and the stepwise 1,2-proton transfer from phenyl ring to amine to restore aromaticity of phenyl ring. We find that both the methoxy Mobius rearrangement and the following stepwise 1,2-proton transfer are the rate-determining steps of the whole reaction in the NHCÀ Ag(I)/Au(I) catalysis systems. Based on our computational results, we predict that 2-methyl-N-methoxyaniline catalyzed by NHCÀ Ag(I)/Au(I) may produce 2methyl-6-methoxyaniline as the major product, which is a double-ortho-and multi-substituted aniline.