The visible-light-promoted intermolecular para-cycloadditions of allenamides on naphthalene

Abstract

The preparation of bridged bicyclooctadienes through the dearomatization of simple arenes is an interesting synthetic tool to access a vast chemical space of elegant molecular architectures from a wide range of simple and cheap building blocks. However, the energetic toll due to the loss of the aromatic stabilization has greatly limited the development of para-cycloadditions, especially with respect to intermolecular processes. We report herein the first general approach for the selective dearomatization of simple naphthalene. The visible-light-promoted reaction occurs under mild conditions over an ample range of substrates and it involves the initial sensitization of an acylallenamide. Moreover, complete control on the difunctionalization of either the internal or the terminal C–C double bond is observed depending on the substrate functionalization.

Keywords

• Allenes
• Cycloadditions
• Dearomatization
• Photocatalysis
• Polycycles