Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization

Abhishek A. Kantak, University of Rhode Island
Shathaverdhan Potavathri, University of Rhode Island
Rose A. Barham, University of Rhode Island
Kaitlyn M. Romano, University of Rhode Island
Brenton Deboef, University of Rhode Island


The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both a N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated. © 2011 American Chemical Society.