Photochemical nucleophile-olefin combination, aromatic substitution reaction. Its synthetic development and mechanistic exploration.

Abstract

The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction has been a cornerstone of research in our laboratory for several years. In this Account we present an overview of the mechanistic exploration and rationalization of this photoinduced electron transfer reaction. We have investigated the mechanism and defined the synthetic scope and limitations by variations in reaction conditions and structural modification of the substrates. During our studies, we have come across several other pathways in competition with the photo-NOCAS reaction that dominate once specific conditions are altered. These alternative reactions are also discussed briefly.