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.

Rhodium‐catalyzed formation of the CN bond by CH activation without using any external oxidant has been summarized in this article. This article mainly deals with Rh(II)‐ and Rh(III)‐catalysis involving the inner‐ and outer‐sphere mechanism, respectively. The aminating agents such as N ‐carboxylates, organic azides, anthranils, dioxazolones, nitrosobenzenes alternative to simple amines (primary) are useful in reducing reaction wastes and add a greener approach under the CH amination and amidation methods. Moreover, a broad functional group tolerance and wide substrate scope are the common features of such CN bond construction reactions.