Rejuvenation of dearomative cycloaddition reactions via visible light energy transfer catalysis

Dearomative cycloaddition is a powerful technique to access sp³-rich three-dimensional structural motifs from simple flat, aromatic feedstock. The building-up of unprecedentedly diverse polycyclic scaffolds with increased saturation and stereochemical information having various applications ranging from pharmaceutical to material sciences, is an essential goal in organic chemistry. However, the requirement of large energy inputs to disrupt the aromaticity of an arene moiety necessitates harsh reaction conditions for ground state dearomative cycloaddition. The photochemical requirement encompasses use of ultraviolet (UV) light to enable the reaction on an excited potential energy surface. The microscopic reversibility under thermal conditions and the use of high energy harmful UV irradiation in photochemical manoeuvres, however, constrain their widespread use from a synthetic point of view. In this context, the recent renaissance of visible light energy transfer (EnT) catalysis has become a powerful tool to initiate dearomative cycloaddition as a greener and more sustainable approach. The excited triplet state population is achieved by triplet energy transfer from the appropriate photosensitizer to the substrate. While employing mild visible light energy as fuel, the process leverages an enormous potential of excited state reactivity. The discovery of an impressive portfolio of organic and inorganic photosensitizers with a range of triplet energies facilitates visible light photosensitized dearomative cycloaddition of various substrates to form sp³-rich fused polycyclic architectures with diverse applications. The tutorial review comprehensively surveys the reawakening of dearomative cycloadditions via visible light-mediated energy transfer catalysis in the past five years. The progress ranges from intra- and intermolecular [2π + 2π] to [4π + 2π], and ends at intermolecular [2π + 2σ] cycloadditions. Furthermore, the review provides potential possibilities for future growth in the growing field of visible light energy transfer catalysis.