Synthesis and Aromaticity of Benzene-Fused Doubly N-Confused Porphyrins.

A bicyclo[2.2.2]octadiene(BCOD)-fused bis(dipyrromethane) derivative was reacted with methylal in the presence of trifluoroacetic acid followed by oxidation with chloranil to give a doubly N-confused phlorin derivative, which did not undergo the retro-Diels-Alder reaction extruding an ethylene molecule on heating. In contrast, a 7- tert -butoxybicyclo[2.2.1]heptadiene(7-BuOBCHD)-fused bis(dipyrromethane) yielded benzene-ring-fused doubly N-confused porphyrins by following similar reaction sequences.

[1]  A. Białońska,et al.  Oxygenation of Phenanthriporphyrin and Copper(III) Phenanthriporphyrin: An Efficient Route to Phenanthribilinones. , 2019, Inorganic chemistry.

[2]  T. Okujima,et al.  Di(acenaphtho)BODIPYs and Dipyrrins as Dyes with Deep-Red To NIR Absorptions , 2019, Bulletin of the Chemical Society of Japan.

[3]  M. Tariq,et al.  Emerging Applications of Porphyrins and Metalloporphyrins in Biomedicine and Diagnostic Magnetic Resonance Imaging , 2018, Biosensors.

[4]  M. Sankar,et al.  Selective Conversion of Planar trans-Chlorins into Highly Twisted Doubly Fused Porphyrins or Chlorins via Oxidative Fusion. , 2018, Inorganic chemistry.

[5]  Qingyun Liu,et al.  Porphyrin-sensitized solar cells: systematic molecular optimization, coadsorption and cosensitization. , 2018, Chemical communications.

[6]  A. Osuka,et al.  Porphyrinoids as a platform of stable radicals , 2018, Chemical science.

[7]  Jung-Ho Hong,et al.  Synthesis of a Phlorin from a Meso-Fused Anthriporphyrin by a Diels-Alder Strategy. , 2017, Angewandte Chemie.

[8]  D. Dou,et al.  Porphyrin photosensitizers in photodynamic therapy and its applications , 2017, Oncotarget.

[9]  J. Mack.  Expanded, Contracted, and Isomeric Porphyrins: Theoretical Aspects. , 2017, Chemical reviews.

[10]  A. Osuka,et al.  Chemistry of meso-Aryl-Substituted Expanded Porphyrins: Aromaticity and Molecular Twist. , 2017, Chemical reviews.

[11]  T. Okujima,et al.  Diethyl N,N′-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate as a 14π-electronic aromatic compound with two azomethine-ylide moieties , 2017 .

[12]  Jung-Ho Hong,et al.  2-(Naphthalen-1-yl)thiophene as a New Motif for Porphyrinoids: Meso-Fused Carbaporphyrin. , 2016, Journal of the American Chemical Society.

[13]  A. Tomé,et al.  Porphyrin Macrocycle Modification: Pyrrole Ring-Contracted or -Expanded Porphyrinoids , 2016, Molecules.

[14]  H. Ågren,et al.  Neo-fused hexaphyrin: a molecular puzzle containing an N-linked pentaphyrin. , 2014, Angewandte Chemie.

[15]  C. Ziegler,et al.  Phlorins bearing different substituents at the sp3-hybridized meso-position. , 2014, The Journal of organic chemistry.

[16]  Justyna Dominikowska,et al.  Aromaticity from the viewpoint of molecular geometry: application to planar systems. , 2014, Chemical reviews.

[17]  D. Gryko,et al.  Electrochemically driven intramolecular oxidative aromatic coupling as a pathway toward π-extended porphyrins. , 2013, Inorganic chemistry.

[18]  J. Sessler,et al.  π-Extended isomeric and expanded porphyrins. , 2013, Chemical Society reviews.

[19]  Hiroki Uoyama,et al.  FACILE SYNTHESIS OF 4,9-DIHYDRO-2H-BENZ[f]- AND 4,11-DIHYDRO-2H-NAPHTH[2,3-f]ISOINDOLES AND THEIR UTILITY FOR PORPHYRIN SYNTHESIS (Dedicated to Dr. Albert Padwa on his 75th birthday) , 2012 .

[20]  M. Baik,et al.  Conformational and electronic consequences in crafting extended, π-conjugated, light-harvesting macrocycles. , 2011, Chemistry.

[21]  M. Pink,et al.  PtCl2-catalyzed benzannulation of nickel(II) 2,3-dialkynylporphyrins to form unusual phenanthroporphyrins , 2011 .

[22]  Lijun Zhu,et al.  BODIPY-fused porphyrins as soluble and stable near-IR dyes. , 2011, Chemistry.

[23]  Jong Min Lim,et al.  Conformation dynamics of non-, singly- and doubly-N-fused [28]hexaphyrins revealed by photophysical studies. , 2011, Chemical communications.

[24]  Jishan Wu,et al.  Doubly and triply linked porphyrin-perylene monoimides as near IR dyes with large dipole moments and high photostability. , 2011, The Journal of organic chemistry.

[25]  H. Anderson,et al.  A porphyrin fused to four anthracenes. , 2011, Journal of the American Chemical Society.

[26]  A. Osuka,et al.  Singly N-fused Möbius aromatic [28]hexaphyrins(1.1.1.1.1.1). , 2010, The Journal of organic chemistry.

[27]  Jishan Wu,et al.  N-annulated perylene fused porphyrins with enhanced near-IR absorption and emission. , 2010, Organic letters.

[28]  H. Furuta,et al.  N-heterocyclic carbene embedded in an N-confused porphyrin framework. , 2010, Inorganic chemistry.

[29]  H. Anderson,et al.  Bis-anthracene fused porphyrins: synthesis, crystal structure, and near-IR absorption. , 2010, Organic letters.

[30]  Anthony L. Spek,et al.  Structure validation in chemical crystallography , 2009, Acta crystallographica. Section D, Biological crystallography.

[31]  Harry L Anderson,et al.  Expanding the porphyrin pi-system by fusion with anthracene. , 2008, Organic letters.

[32]  J. Aihara,et al.  Aromaticity and magnetotropicity of dicyclopenta-fused polyacenes. , 2008, Physical chemistry chemical physics : PCCP.

[33]  M. Stillman,et al.  Application of MCD spectroscopy to porphyrinoids , 2007 .

[34]  Dongho Kim,et al.  A quadruply azulene-fused porphyrin with intense near-IR absorption and a large two-photon absorption cross section. , 2006, Angewandte Chemie.

[35]  R. Herges,et al.  Anisotropy of the induced current density (ACID), a general method to quantify and visualize electronic delocalization. , 2005, Chemical reviews.

[36]  D. Gryko,et al.  Isolation of Phlorin-Dipyrrin Conjugates from the Acid-Catalyzed Condensation of Dipyrromethanes and Aldehydes , 2005 .

[37]  Masaaki Suzuki,et al.  Doubly N-fused meso-aryl substituted hexaphyrins(1.1.1.1.1.1). , 2004, Chemical communications.

[38]  M. Nishio.  CH/π hydrogen bonds in crystals , 2004 .

[39]  M. Yamashita,et al.  Pyrene-Fused Porphyrins: Annulation Reactions of meso-Pyrenylporphyrins , 2004 .

[40]  M. Nguyen,et al.  Density functional studies on N-fused porphyrin. Electronic, magnetic and metal binding properties , 2002 .

[41]  Y. Ishikawa,et al.  NH tautomerism of N-confused porphyrin. , 2001, Journal of the American Chemical Society.

[42]  S. Ito,et al.  Synthesis and structures of pyrroles fused with rigid bicyclic ring systems at β-positions , 2000 .

[43]  A. Battersby.  Tetrapyrroles: the pigments of life. , 2000, Natural product reports.

[44]  Christopher A. Hunter,et al.  The nature of .pi.-.pi. interactions , 1990 .

[45]  J. Michl.  Electronic structure of aromatic π-electron systems as reflected in their MCD spectra , 1980 .

[46]  J. Michl.  Magnetic circular dichroism of cyclic .pi.-electron systems. 2. Algebraic solution of the perimeter model for the B terms of systems with a (4N + 2)-electron [n]annulene perimeter , 1978 .

[47]  J. Michl.  Magnetic circular dichroism of cyclic .pi.-electron systems. 1. Algebraic solution of the perimeter model for the A and B terms of high-symmetry systems with a (4N + 2)-electron [n]annulene perimeter , 1978 .

[48]  Martin Gouterman,et al.  Spectra of porphyrins: Part II. Four orbital model , 1963 .