First α-deuterium nitroxides; synthesis and EPR study.

Herein is reported the first preparation of stable α-deuterium nitroxides of the IAPNO family. The confirmation and characteristics of the α-deuterium nitroxides and their α-hydrogen analogues are compared and analyzed. Such α-deuterium nitroxides may find use in biology, medicine and physical chemistry.

Synthesis and stability of cyclic α-hydrogen nitroxides.

Nitroxides (nitroxyl radicals) hold a unique place in science due to their stable radical nature. We have recently reported the first design concept providing a general solution to the problem of designing and preparing monocyclic α-hydrogen nitroxides. The initial studies were limited to aryl derivatives.

Design concept for α-hydrogen-substituted nitroxides.

Stable nitroxides (nitroxyl radicals) have many essential and unique applications in chemistry, biology and medicine. However, the factors influencing their stability are still under investigation, and this hinders the design and development of new nitroxides. Nitroxides with tertiary alkyl groups are generally stable but obviously highly encumbered.

Organocatalytic oxidation of aldehydes to mixed anhydrides.

TEMPO catalyzes the direct oxidation of aldehydes to mixed anhydrides in the presence of a carboxylic acid. The anhydrides can be converted in situ to esters, secondary, tertiary or Weinreb amides in high yield. Oxidation of the aldehyde directly to 2-propyl esters is also possible using only catalytic amounts of acid.