The development of an oriented arylation process dedicated to the naphthalene core is presented. Our approach is based on dual role of N‐tosyl carboxamides acting jointly as a directing group in a first C–H arylation step and as a “CO” or “CO–NH” fragment precursor in a further construction step of naphthalene‐based fluorenone or phenanthridinone derivatives. The presence of the directing group in position 1 and 2 of the naphthalene platform allowed selective arylations in position 2 and 3 respectively. Our study represents a first synthetic and general entry of C–H arylation at naphthalene platforms towards the preparation of extended fluorenones as well as benzo‐fused phenanthridinones. Further, the C–H arylation and cyclisation sequence represents a useful way to the preparation of novel extended tetra‐ and pentacyclic fluorenones bearing both electron donating as well as electron withdrawing groups in various substitution patterns. Additionally, both the regioselectivity and the reaction paths of the cyclization leading to the fluorenone architectures was studied by DFT calculations which fully complement experimental observations.

A highly efficient pyridylmethylamine‐Pd alternative catalytic system for the C−H arylation of indole was explored. Variously substituted aryl groups were regio‐ and chemoselectively installed at the indole nucleus by using barium hydroxide as the base. The method was found to be efficient even in the presence of hindered coupling partners and Pd‐reactive bonds.

Naphthalene is certainly not a common arene. In contrast to benzene, the bicyclic feature of naphthalene offers multiple differentiable positions and thus a broad diversity of substitution patterns. Naphthalene is a central building block for the construction of elaborated polycyclic architectures with applications in broad domains such as life and materials sciences. As a result, C–H functionalization strategies specially designed for naphthalene substrates have become essential to install valuable substituents on one or both rings towards polysubstituted naphthalenes. This short review provides a focus on uncommon substitution patterns; however, classical ortho C–H activation is not covered.1 Introduction2 C–H Functionalization Using a Directing Group Located at Position 12.1 Functionalization on the Ring Bearing the DG: 1,3-Substitution Pattern2.2 Functionalization on the Ring Bearing the DG: 1,4-Substitution Pattern2.3 Functionalization on the Neighboring Ring: 1,6-, 1,7- and 1,8-Substitution Patterns3 C–H Functionalization Using a Directing Group Located at Position 23.1 Functionalization on the Ring Bearing the DG: 2,4- and 2,1-Substitution Patterns3.2 Miscellaneous Substitution Patterns4 Bis C–H Functionalization4.1 Symmetrical Bisfunctionalization: 1,2,8-Substitution Pattern4.2 Symmetrical Bisfunctionalization: 2,3,1-Substitution Pattern4.2 Unsymmetrical Bisfunctionalization: 2,3,1-Substitution Pattern4.3 Symmetrical Bisfunctionalization: 2,4,8-Substitution Pattern5 Conclusion and Outlook