Transition-Metal- and Light-Free Generation of an Iminyl Radical: Facile Approach to Oxindoles and Isoquinolinediones with a Quaternary Carbon Center via Cyanoalkylarylation.

We have developed an efficient and non-toxic method for the environmental-friendly generation of an iminyl radical from cyclobutanone oxime ester via direct thermolysis in the absence of light, transition metals, "tin", and other activators. This redox-neutral cyanoalkylarylation protocol enjoys a wide substrate scope and a good functional group tolerance, providing facile access to oxindoles and isoquinolinediones with a quaternary carbon center that are difficult to prepare by traditional methods.

Construction of Quaternary Carbon Center via NHC Catalysis Initiated by an Intermolecular Heck-Type Alkyl Radical Addition.

A quaternary carbon center containing an oxindole motif is constructed via NHC-catalyzed transition-metal and aldehyde-free intermolecular Heck-type alkyl radical addition initiated annulation. This redox-neutral protocol also features a simple procedure, broad substrate scope, good functional group tolerance and could be smoothly amplified to a gram scale. The mechanism study shows that the reaction possibly undergoes two folds of SET processes with an NHC radical cation intermediate involved.