A Facile One-Pot Synthesis of meso-Aryl-Substituted [14]Triphyrin(2.1.1)

Abstract

The synthesis and spectroscopic properties of a series of boron-free meso-aryl-substituted [14]triphyrin(2.1.1) compounds containing either peripheral bicyclo[2.2.2]octadiene (BCOD) (2a−c) or benzene rings (3a−c) (aryl = phenyl a, 4-fluorophenyl b, and 4-methylbenzoatephenyl c) are reported. These compounds represent the first examples of free-base contracted porphyrinoids with 14 π-electron aromatic systems containing only the standard pyrrole and isoindoline moieties of the porphyrins and tetrabenzoporphyrins.

Oxatriphyrins(2.1.1) Incorporating an ortho‐Phenylene Motif

“…Such an effect is typical for triphyrins(n.1.1). [9,10] The electronic spectrum of 2-H is consistent with the NMR-derived conclusions. An intense Soret-like band is accompanied by a set of Q-bands (Figure 2).…”

“…The behavior resembles that of other triphyrins(n.1.1). [10] To explore the wider applicability of the presented synthetic approach, the calix-triphyrin 4 was synthesized and used here as an appropriate reference point to analyze macrocyclic conjugation. The synthetic approach involves the same strategy as that applied for 2-H, but using 2,5-bis(hydroxydiphenylmethyl)furan (Scheme 1).…”

Annulation and Arylation Stabilize New Porphyrinoids

“…[1] It is closely related to the abovementioned triaryl tribenzosupporphyrin 3, but carries a (2.1.1) bridge pattern. [1] It is closely related to the abovementioned triaryl tribenzosupporphyrin 3, but carries a (2.1.1) bridge pattern.…”

“…Porphyrin research keeps up in presenting astonishing results, which is aptly demonstrated by the synthesis of a new free-base (non-metalated) [14]triphyrin(2.1.1) [1] and the very recent formation of tetraazuliporphyrin tetracation. [2] Both compounds owe their stablity to annulation and arylation of the aromatic skeleton with other p-electron-rich rings.…”

Women in Chemistry

“…In 2008, we reported the first serendipitous synthesis of free-base [14]triphyrinA C H T U N G T R E N N U N G (2.1.1) compounds during a BF 3 ·Et 2 O-catalyzed Lindsey reaction. [7] In contrast to the previously reported subporphyrins which contain a central boron with a bowlshaped conformation, this new triphyrin system may allow new, unique metal complexation behavior in subporphyrin chemistry, together with applications thereof, to be explored for the first time (highlighted by Norbert Jux in Angewandte Chemie [8] ). Although the Lindsey method has been widely used for the synthesis of tetrapyrrole [18]porphyrin over the decades, no triphyrin compounds have ever been reported before.…”