Abstract
We report the first examples of radical cation Smiles rearrangements. A series of aryloxy alkylamines underwent spontaneous reaction, with the amino group displacing the ipso-alkoxy group through substitution, at ambient temperature and under photoactivation by visible light in the presence of an acridinium catalyst (5 mol%). The study was extended to 3-(2-methoxyphenyl)propan-1-amine derivatives, which lack an appropriate ipso leaving group. Here, efficient cyclisations resulted in displacement of the methoxy group and formation of tetrahydroquinolines.
Highlights
We report the first examples of radical cation Smiles rearrangements
A series of aryloxy alkylamines underwent spontaneous reaction, with the amino group displacing the ipso-alkoxy group through substitution, at ambient temperature and under photoactivation by visible light in the presence of an acridinium catalyst (5 mol%)
Efficient cyclisations resulted in displacement of the methoxy group and formation of tetrahydroquinolines
Summary
We report the first examples of radical cation Smiles rearrangements. Inspired by recent developments in the Newman–Kwart rearrangement, where chemical, photochemical and electrochemical methods for single-electron oxidation enhanced reactivity, we proposed a radical cation approach to the Smiles rearrangement.[18] We show that a range of aryloxy alkylamines successfully undergo a mild and efficient photo-Smiles rearrangement using an acridinium salt as the organophotoredox catalyst (Scheme 1c).
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