Annulative π-extension (APEX) reaction has become a powerful tool for the precise synthesis of welldefined polycyclic aromatic hydrocarbons (PAHs) such as nanographene, graphene, and other PAHs possessing unique structure. Herein, an APEX reaction has been realized at the masked bay-region for the efficient and rapid synthesis of valuable PAH, pyrene, bearing substitutions at the most challenging K-region. Rh IIIcatalyzed ketone-directed CÀ H activation at the periposition of a naphthyl-derived ketone, alkyne-insertion, intramolecular nucleophilic attack at the carbonylgroup, dehydration, and aromatization steps occurred in one-pot to effectuate the protocol. Employing this strategy, a two-fold APEX reaction on enantiopure BINOL-derived ketones provided access to axiallychiral bipyrene derivatives. The detailed DFT study to support proposed mechanism, and synthesis of helical PAHs like dipyrenothiophene and dipyrenofuran are other highlights of the present study.

Annulative π-extension (APEX) reaction has become a powerful tool for the precise synthesis of welldefined polycyclic aromatic hydrocarbons (PAHs) such as nanographene, graphene, and other PAHs possessing unique structure. Herein, an APEX reaction has been realized at the masked bay-region for the efficient and rapid synthesis of valuable PAH, pyrene, bearing substitutions at the most challenging K-region. Rh IIIcatalyzed ketone-directed CÀ H activation at the periposition of a naphthyl-derived ketone, alkyne-insertion, intramolecular nucleophilic attack at the carbonylgroup, dehydration, and aromatization steps occurred in one-pot to effectuate the protocol. Employing this strategy, a two-fold APEX reaction on enantiopure BINOL-derived ketones provided access to axiallychiral bipyrene derivatives. The detailed DFT study to support proposed mechanism, and synthesis of helical PAHs like dipyrenothiophene and dipyrenofuran are other highlights of the present study.

Looking into the increasing requirement for sustainable and environmentally sound chemical processes, employing nonprecious metals, specifically the earth‐abundant ones, is an attractive choice to construct CN bond by CH activation strategy involving the inner‐ or outer‐sphere mechanism. The article described Co(II)–porphyrins and cyclopentadienyl‐ligand‐based catalysts as the new class of effective catalysts for the amination or amidation of C(sp 2 /sp 3 )H bonds, with prominence to access a wide array of nitrogen‐containing compounds including heterocycles, natural products, medicinally significant bioactive molecules, and synthetic intermediates.