Abstract
Photocycloadditions of benzene derivatives with alkenes play an important role as key steps in organic synthesis. Intramolecular reactions have been most frequently studied in this context. Often, meta or [2 + 3] photocycloadditions take place in competition with ortho or [2 + 2] additions. The influence of the substitution pattern and the spin multiplicity of the excited state on the outcome of these reactions is discussed. A topological analysis permitting a systematic application of the [2 + 3] photocycloadditions to the total synthesis of natural products is presented and a selection of corresponding syntheses is discussed. More recently the [2 + 2] photocycloaddition and consecutive rearrangements on organic synthesis have been published. Some approaches in the context of asymmetric synthesis have also been reported.
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