Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization.
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.
Department of Chemistry, University of Rhode Island, 51 Lower College Road, Kingston, Rhode Island 02881, USA.
Abhishek A
AA
Kantak
Shathaverdhan
S
Potavathri
Rose A
RA
Barham
Kaitlyn M
KM
Romano
Brenton
B
DeBoef
D000586:Amination; D000814:Aniline Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D055772:Green Chemistry Technology / Q000191:economics / Q000379:methods*; D010084:Oxidation-Reduction; D010797:Phthalimides / Q000138:chemical synthesis / Q000737:chemistry
D000814:Aniline Compounds; D010797:Phthalimides; C037431:phthalimide