We report that the organic superbase t-Bu-P4 efficiently catalyzes the amination of methoxy(hetero)arenes with amine nucleophiles such as aniline, indoline, and aminopyridine derivatives. This catalytic reaction is effective for the transformation of electron-deficient methoxyarenes possessing diverse functionalities (carbonyl, cyano, nitro, and halogen) as well as methoxyheteroarenes, including pyrazine, quinoline, isoquinoline, and pyridine derivatives. Intramolecular reactions provide six-and seven-membered ring cyclic amine products.

The organic superbase tBu-P4 catalyzes methoxy-alkoxy exchange reactions on (hetero)arenes with alcohols. The catalytic reactionp roceedede fficiently with electron-deficient methoxy(hetero)arenes as wella sw ith a variety of alcohols, including 3-amino-1-propanol, b-citronellol, menthol, and cholesterol. An intramolecular version of this reactionf urnished six-and seven-membered ring compounds.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

We describe the catalytic amination of β-(hetero)­arylethyl ethers with amines using the organic superbase t-Bu-P4 to obtain β-(hetero)­arylethyl­amines. The reaction has a broad substrate scope and allows the transformations of electron-deficient and electron-neutral β-(hetero)­arylethyl ethers with various amines including pyrrole, N-alkylaniline, diphenylamine, aniline, indole, and indoline derivatives. Mechanistic studies indicate a two-reaction pathway of MeOH elimination from the substrate to form a (hetero)­arylalkene followed by the hydroamination of the alkene.

Iodoarenes and C−H heteroarenes are coupled to form a biaryl in the presence of an amide base generated in situ from tetramethylammonium fluoride (TMAF) and hexamethyldisilazane (HMDS) by homolytic aromatic substitution (HAS). This reaction can be used with electron‐rich, ‐deficient, and ortho‐substituted haloarenes. Both electron‐rich and ‐deficient C−H heteroarenes can also be utilized. Involvement of a radical intermediate was confirmed by radical inhibition experiments, deuterium‐labelling experiments, and EPR spectral measurements. Enhancement of the reactivity of electron‐rich N‐methylpyrrole was observed in the presence of electron‐poor phenazine or pyrazine.

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