Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs

Abstract

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S-shaped aza[5]helicene.

Polycyclic Aromatic Hydrocarbon‐/Heterocycle‐Embedded Porphyrinoids

“…Latos-Grażyński and co-workers synthesized N-fused-5,6dimethoxyphenanthrihexaphyrins 76 and 77 as shown in Scheme 19. [35] The tripyrrane 44 was treated with 21 f and pnitrobenzaldehyde under mild acid-catalyzed conditions to afford mono-fused 5,6-dimethoxyphenanthrihexaphyrin 76 in 2.2% yield. Furthermore, the authors treated 76 with BF 3 .OEt 2 in the presence of triethylamine in toluene under reflux conditions to obtain bis-N-fused 5,6-dimethoxyphenanthrihexaphyrin 77 in 60% yield.…”

“…Latos‐Grażyński and co‐workers synthesized N ‐fused‐5,6‐dimethoxyphenanthrihexaphyrins 76 and 77 as shown in Scheme . The tripyrrane 44 was treated with 21 f and p ‐nitrobenzaldehyde under mild acid‐catalyzed conditions to afford mono‐fused 5,6‐dimethoxyphenanthrihexaphyrin 76 in 2.2% yield.…”

Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs

“…Thed efinitive confirmation of the 7 H2 structure was provided by X-ray diffraction analysis. [21] Thecrystal contains a1 :1 mixture of enantiomers of 7 H2 .I nt he solid state the molecule 7 H2 retains the figure-of-eight conformation detected in solution ( Figure 3). TheC 31-C1 and C15-C16 bond lengths are equal to 1.483 (5) tively,thus indicating that the helicene is connected to the F-G-H tripyrrolic fragment through as ingle and double bond, respectively.T he average torsion angle in the bay-region of the helicene unit equals 18.98 8,a nd resembles the degree of distortion observed for [4]helicene (198 8).…”

“…[21] tively,thus indicating that the helicene is connected to the F-G-H tripyrrolic fragment through as ingle and double bond, respectively.T he average torsion angle in the bay-region of the helicene unit equals 18.98 8,a nd resembles the degree of distortion observed for [4]helicene (198 8). [21] tively,thus indicating that the helicene is connected to the F-G-H tripyrrolic fragment through as ingle and double bond, respectively.T he average torsion angle in the bay-region of the helicene unit equals 18.98 8,a nd resembles the degree of distortion observed for [4]helicene (198 8).…”

Expanded Porphyrin Contraction: From [22]Triphyrin(6.6.0) to [22]Triphyrin(6.5.0)

“…[2,3] In fact, in the latter approach, the buildingb locks assemblyi sg overned by thermodynamic and kinetic factors and have been fruitful throughout the porphyrinoid chemistry.H owever,a ccessibilityo fd esired building blocks furnished with appropriate side groups capable of buildingc onnections with otheru nits may be low.T hus, another approach, based on the post-synthetic transformations of am acrocyclic skeletonm ay be more efficient and lead to structuresd ifficultt oo btain by assemblyo fs mall units. [4][5][6] Skeletal rearrangementsa re encountered rather rarely; they may be exemplified by ac ore heteroatom replacement [7] or extrusion, [8][9][10] macrocyclic fusion, [11,12] and ring expansion [6,13,14] or contraction.F or porphyrinoid aromatic macrocyclesacontraction may take place at both-a meso-link [6,[15][16][17][18][19] or at ac yclic subunit, like ap yrrole in ar egularp orphyrin, [20,21] ap henylene ring in benziporphyrin [22][23][24][25][26] or naphthiporphyrin, [27] or at the [a] Dr.E.…”