5.15 The Arene–Alkene Photocycloaddition

Abstract

Arene–alkene cycloadditions provide efficient synthetic access to complex polycyclic molecular structures, natural, and nonnatural products, from readily available starting materials. The rise in molecular complexity in the course of these reactions is unprecedented in organic synthesis and makes them a strategic-level transformation for organic synthesis. Wender et al. brought the attention of the synthetic community to this reaction by successful applications to several highly elegant total syntheses of natural products. The following chapter puts a strong emphasis on the meta photocycloaddition. It discusses these reactions briefly from a theoretical standpoint, and moves on to mechanistic considerations. The main part highlights the applications in total synthesis, aiming to provide the reader with an overview over structurally diverse starting materials that have been used in the course of this reaction on one hand and the vast molecular diversity and complexity of products that could be obtained thereof on the other hand.