Synthesis and Reactivity of 5,10,15‐Triaryl Doubly N‐Confused Bilanes

Toganoh, Motoki; Gokulnath, Sabapathi; Kawabe, Yasunori; Furuta, Hiroyuki

doi:10.1002/chem.201103034

Cited by 24 publications

(13 citation statements)

References 79 publications

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“…Recently, elegant syntheses of ABCD‐bilanes from dipyrromethanes by a stepwise acylation/reduction sequence were reported by Lindsey and co‐workers 13d,f . N ‐Confused bilanes have also been prepared by Furuta and co‐workers using an analogous approach 33b. Still, the straightforward nature of the condensation reaction in a water/methanol mixture seemed for us to be the most promising starting point.…”

Section: Resultsmentioning

confidence: 99%

An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media

Nowak‐Król

Plamont

Canard

et al. 2014

Chemistry A European J

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We have developed new conditions that afford regioisomerically pure trans-A2B2-, A3B-, and trans-AB2C-porphyrins bearing aryl and arylethynyl substituents. The porphyrins were prepared by the acid-catalyzed condensation of dipyrromethanes with aldehydes followed by oxidation with p-chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Optimal conditions for the condensation were identified after examining various reaction parameters such as solvent composition, acid concentration, and reaction time. The conditions identified (for aromatic aldehydes: EtOH/H2O 4:1, [DPM] = 4 mM, [aldehyde] = 4 mM, [HCl] = 38 mM, 16 h; for arylethynyl aldehydes: THF/H2O 2:1, [DPM] = 13 mM, [aldehyde] = 13 mM, [HCl] = 150 mM, 3 h) resulted in the formation of porphyrins in yields of 9-38% without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans-A2B2-, A3B-, and trans-AB2C-porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in higher yields than by any other methodology and by using environmentally benign and nonhazardous chemicals.

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Section: Resultsmentioning

confidence: 99%

An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media

Nowak‐Król

Plamont

Canard

et al. 2014

Chemistry A European J

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“…Due to the possibility of interconnecting pyrrole rings through different groups, expanded tetrapyrrole macrocycles have been synthesized [ 185 , 186 , 187 , 188 , 189 ]. Due to all the physicochemical and technological implications of the natural or synthetic pyrrole derived compounds, new compounds such as synthetic bilanes [ 190 ] and biliverdins [ 191 ], as well as oligo- or polypyrroles [ 192 ] have been synthesized.…”

Section: Synthetic Porphyrins and Phthalocyaninesmentioning

confidence: 99%

Crossed and Linked Histories of Tetrapyrrolic Macrocycles and Their Use for Engineering Pores within Sol-Gel Matrices

et al. 2013

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The crossed and linked histories of tetrapyrrolic macrocycles, interwoven with new research discoveries, suggest that Nature has found in these structures a way to ensure the continuity of life. For diverse applications porphyrins or phthalocyanines must be trapped inside solid networks, but due to their nature, these compounds cannot be introduced by thermal diffusion; the sol-gel method makes possible this insertion through a soft chemical process. The methodologies for trapping or bonding macrocycles inside pristine or organo-modified silica or inside ZrO2 xerogels were developed by using phthalocyanines and porphyrins as molecular probes. The sizes of the pores formed depend on the structure, the cation nature, and the identities and positions of peripheral substituents of the macrocycle. The interactions of the macrocyclic molecule and surface Si-OH groups inhibit the efficient displaying of the macrocycle properties and to avoid this undesirable event, strategies such as situating the macrocycle far from the pore walls or to exchange the Si-OH species by alkyl or aryl groups have been proposed. Spectroscopic properties are better preserved when long unions are established between the macrocycle and the pore walls, or when oligomeric macrocyclic species are trapped inside each pore. When macrocycles are trapped inside organo-modified silica, their properties result similar to those displayed in solution and their intensities depend on the length of the alkyl chain attached to the matrix. These results support the prospect of tuning up the pore size, surface area, and polarity inside the pore cavities in order to prepare efficient catalytic, optical, sensoring, and medical systems. The most important feature is that research would confirm again that tetrapyrrolic macrocycles can help in the development of the authentic pore engineering in materials science.

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“…In this respect, by incorporation of "mislinked" pyrrole rings, in what we call the "confusion approach", [3] a variety of novel porphyrin analogues have been developed with unique properties. [4][5][6][7][8][9][10] Typical examples include N-confused porphyrin, [4] N-fused porphyrin, [5] corrorin, [6] neo-confused corrole (norrole), [8] neo-confused porphyrin, [9] and expanded norrole (Scheme 1). [10] In these compounds, the confused pyrrole units are linked in the a,b '-mode (confused) or N,b-mode (neo-confused).…”

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confidence: 99%

“…The best evidence for the formation of CÀN bonds in the macrocyclic structures of 1 and 2 came from the crystal structures [14] (Figure 2). Interestingly, the bipyrrole rings in 1 are directly linked in a unique b,N-a,b mode, which bears similarity to the bonding mode in neo-confused corrole (norrole) [8] and corrorin, [6] and thus 1 is named neo-confused hexaphyrin(1.1.1.1.1.0).…”

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confidence: 99%

Neo‐Fused Hexaphyrin: A Molecular Puzzle Containing an N‐Linked Pentaphyrin

Wei

Zhang

et al. 2014

Angew Chem Int Ed

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The first neo-confused hexaphyrin(1.1.1.1.1.0) was synthesized by oxidative ring closure of a hexapyrrane bearing two terminal "confused" pyrroles. The new compound displays a folded conformation with a short interpyrrolic C⋅⋅⋅N distance of 3.102 Å, and thus it readily underwent ring fusion to afford a neo-fused hexaphyrin with an unprecedented 5,5,5,7-tetracyclic ring structure. Furthermore, coordination of Cu(II) triggered a ring opening/contracting reaction to afford a Cu(II) complex of an N-linked pentaphyrin derivative. The roles of reactive N-C bonds in the porphyrinoid macrocycles were demonstrated.

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Synthesis and Reactivity of 5,10,15‐Triaryl Doubly N‐Confused Bilanes

Cited by 24 publications

References 79 publications

An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media

An Efficient Synthesis of Porphyrins with Different meso Substituents that Avoids Scrambling in Aqueous Media

Crossed and Linked Histories of Tetrapyrrolic Macrocycles and Their Use for Engineering Pores within Sol-Gel Matrices

Neo‐Fused Hexaphyrin: A Molecular Puzzle Containing an N‐Linked Pentaphyrin

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