RESUMO
Stable nitroxyl radical-containing compounds, such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and its derivatives, are capable of electrocatalytically oxidizing a wide range of alcohols under mild and environmentally friendly conditions. Herein, we examine the structure-function relationships that determine the catalytic activity of a diverse range of water-soluble nitroxyl radical compounds. A strong correlation is described between the difference in the electrochemical oxidation potentials of a compound and its electrocatalytic activity. Additionally, we construct a simple computational model that is able to accurately predict the electrochemical potential and catalytic activity of a wide range of nitroxyl radical derivatives.
RESUMO
Aminal radicals were generated by reduction of the corresponding amidine or amidinium ion. The intermediate radicals participate in C-C bond-forming reactions to produce fully substituted aminal stereocenters. No toxic additives or reagents are required. More than 30 substrate combinations are reported, and chemical yields are as high as 99%.
Assuntos
Amidinas/química , Amidinas/síntese química , Carbono/química , Catálise , Estrutura Molecular , EstereoisomerismoRESUMO
Aminal radicals were generated by radical translocation processes. For the first time, it is shown that they participate in carbon-carbon bond forming reactions. Either stannane or silane hydrogen atom donors are suitable for the reaction. More than 30 substrate combinations are reported, and chemical yields are as high as 91%.