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

ABSTRACT: 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.

SUBMITTER: Kantak AA

PROVIDER: S-EPMC3233640 | biostudies-literature | 2011 Dec

REPOSITORIES: biostudies-literature

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

Kantak Abhishek A AA Potavathri Shathaverdhan S Barham Rose A RA Romano Kaitlyn M KM DeBoef Brenton B

Journal of the American Chemical Society 20111116 49

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 aromati ...[more]

PMID: 22010982

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