Synthesis of Dioxa-1,7-naphthicorrole and Its Oxidized Porphyrinoid as a Potential Built-In Linker for Biomolecules

Abstract

The first aromatic benzicorrole termed naphthicorrole was synthesized with a carbon donor containing more than six members. Its oxidized (enedione-embedded) porphyrinoid was also obtained using different meso-aryl substitutions under sequential oxidation conditions. The resulting enedione motif of the nonaromatic porphyrinoid was regioselective to the C2 position for S or N nucleophiles. Thus, the oxidized porphyrinoid was tested as a built-in linker for biomolecules. The progress of the reaction was visually monitored due to their different conjugation pathways.

Porphyrinoid framework embedded with polycyclic aromatic hydrocarbons: new synthetic marvels

“…Cho and co-workers 36 were also successful in synthesizing dioxa-1,7-naphthicorrole 63b and oxidized porphyrinoid 63a , as shown in Scheme 12(i). Initially, they attempted to synthesize dioxa-1,7-naphthicorrole 63b in three steps starting with 1,7-dibromonaphthalene 64 .…”

Unsymmetrization of 1,8-Dibromonaphthalenes by Acid-Induced Halogen Dance Reaction

“…For identification of products 3 8 and 4, 9 their 1 H NMR spectra were compared with authentic examples. The assignments of the 13 C{ 1 H} NMR spectra were performed by DEPT experiments. High-resolution mass analysis was performed by a Bruker compact mass spectrometer set at APCI-negative mode.…”

Fundamental difference between simple arenes and PAHs found in o-PAH-connected porphyrins

“…In addition, we investigated the properties of π-extended forms of o-benzene-connected porphyrin. Expansions of porphyrinoids have also drawn significant attention because of their unique reactivity, [9][10][11][12] different π-conjugation pathways and related spectral properties, 13,14 various levels of aromaticity, [15][16][17] applications as metal-selective sensors, 18,19 and uncommon oxidation states of their metal complexes. 20 Herein, we report an unexpected reduction in aromaticity when simple arenes are replaced with polycyclic aromatic hydrocarbons (PAHs) in o-arene-connected porphyrins (Fig.…”