Synthesis of Pyrrolidine-Fused [34]- and [36]Octaphyrins via 1,3-Dipolar Cycloaddition

Abstract

[reaction: see text] The utility of expanded porphyrins as a dipolarophile in cycloaddition reactions has been investigated. The 1,3-dipolar cycloaddition of meso-octakis(pentafluorophenyl)[36]octaphyrin(1.1.1.1.1.1.1.1) with an azomethine ylide provides mono- and bis-pyrrolidine-fused octaphyrins regio- and stereoselectively. Treatment of the cycloadduct with MnO(2) afforded [34]octaphyrin quantitatively.

Figure Eights, Möbius Bands, and More: Conformation and Aromaticity of Porphyrinoids

“…(Scheme 23). [67,100,103,238,264,265] Figure-eight conformers have also been reported for certain heteroanalogues of the above systems (86, 87, and 88-H 2 ). [126,257] Representative examples of all-pyrrole structures are shown in Figure 14.…”

“…[265] The latter species was oxidized with MnO 2 to give its 34-electron counterpart, 91e-H 2 . All three systems were characterized crystallographically and found to adopt a T2 0 conformation that is distinct from the parent structure 81e-H 4 .…”

Figure‐Eight‐Strukturen, Möbius‐Bänder und mehr: Konformation und Aromatizität von Porphyrinoiden

“…[67,100,103,238,264,265] Auch manche Heteroanaloga dieser Systeme (86, 87 und 88-H 2 ) haben die Figure-EightKonformation. [126,257] Untereinheiten.…”

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

“…The discovery of sapphyrins and expanded porphyrins have attracted the interest of researchers attributed to their diverse applications in materials science (Sprutta and Latos-Grazyński, 2001; Flemming and Dolphin, 2002; Pushpan et al, 2002; Silva et al, 2002a,b; Cavaleiro et al, 2003; Hata et al, 2006; Tanaka and Osuka, 2016). The defining feature of these macrocycles is the presence of a larger internal cavity as compared to those present in natural tetrapyrroles.…”

“…The defining feature of these macrocycles is the presence of a larger internal cavity as compared to those present in natural tetrapyrroles. More specifically, expanded porphyrins are macrocyclic compounds containing five-membered heterocyclic units (like pyrrole, furan, or thiophene) linked together, either directly or through spacers with internal ring pathway contains at least 17 atoms (Sprutta and Latos-Grazyński, 2001; Flemming and Dolphin, 2002; Pushpan et al, 2002; Silva et al, 2002a,b; Hata et al, 2006). Their distinctive physical and structural properties have found applications in nonlinear optical (NLO) materials (Marder et al, 1997; Zhou et al, 2002; Ahn et al, 2005; Rath et al, 2005a; Misra et al, 2006), photosensitizers for photodynamic therapy (PDT) (Harriman et al, 1989; Maiya et al, 1989), transition or rare earth metal ion chelates, cation and anion receptors (Shionoya et al, 1992; Jasat and Dolphin, 1997; Sessler et al, 2000a,b; Sessler and Davis, 2001; Chandrashekar and Venkatraman, 2003), magnetic resonance imaging (MRI) contrasting agents (Charrière et al, 1993; Weghorn et al, 1996; Werner et al, 1999) and a tool for accessing presently unknown higher aromatic systems (Sessler et al, 1993).…”