Development of new chemistries of photogenerated distonic radical cations: From mechanistic investigations to synthetic applications.

by Zheng, Nan

Amines are routinely used in photoredox catalysis as an electron donor to reduce the photoexcited state of organometallic complexes or org. dyes while they are oxidized to amine radical cations. Taking advantage of this facile redox process, we have applied it to ring opening of cyclopropylanilines and cyclobutylanilines, which produces distonic radical cations. These reactive species bearing a spatially sepd. iminium ion and a carbon radical, undergo annulation reactions with various types of pi bonds to yield a range of aniline-substituted carbocycles. We investigated one of the annulation reactions, the [3+2] annulation of cyclopropylanilines with alkenes using online mass spectrometry coupled with online laser irradn. The results from this investigation helped us develop a new reaction, difunctionalization of cyclopropylanilines and cyclobutylanilines in which the bimodal reactivity of the distonic radical cations is fully captured.