A Benzodipyrrole‐Derived Sapphyrin

Panda, Pradeepta K.; Kang, Youngjin; Lee, Changhee

doi:10.1002/anie.200500944

Cited by 57 publications

(44 citation statements)

References 24 publications

(17 reference statements)

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“…[62] The benzosapphyrin 61 was also prepared by a stepwise route from 59 and 60 (Scheme 12). [63] The N-confused sapphyrin 64 was prepared by the oxidative ringclosure reaction of the pentapyrrole compound or the "3+2" condensation reaction of 62 and 63 (Scheme 12). [64] As a different but quite effective protocol, Sessler and coworkers employed a reversible imine-forming reaction to fulfill the final cyclization reaction of Schiff base macrocycles such as texaphyrin 13 (Scheme 13).…”

Section: Stepwise Synthesismentioning

confidence: 99%

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

2011

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The chemistry of expanded porphyrins, which are higher homologues of porphyrins, has been intensively explored for the last three decades. Expanded porphyrins exhibit structures, electronic properties, coordination chemistry, and reactivities that are entirely different from those of porphyrins. Through these studies, it has become increasingly apparent that expanded porphyrins are attractive in views of aromaticity and multimetal coordination, or as functional dyes, nonlinear optical materials, ion receptors, or stable organic radicals. As such, we have continuously witnessed the emergence of expanded porphyrins that exhibit unprecedented structures and properties, as is highlighted by the facile realization of Möbius aromatic and even antiaromatic systems with twisted molecular structures. In this Review, the recent progress of the chemistry of expanded porphyrins after the seminal Review by Sessler and Seidel in 2003 is presented.

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Section: Stepwise Synthesismentioning

confidence: 99%

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

2011

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“…[12] Since then, sapphyrins have remained at opic of high interest, [13][14][15][16] in part because of their potential applicationsi nt he area of photodynamic therapy and their structurals imilarity to the well-known porphyrin and corrole macrocycles, [10,11,[17][18][19][20][21] and in part because of their unique properties as ar eceptor of neutraland anionic substrates. [22][23][24][25][26][27][28][29] Al arge number of studies have characterizedd ifferent sapphyrind erivatives, including b-alkylateds apphyrins, [30][31][32][33] coremodified sapphyrins with heteroatoms (O, S, or Se), [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] Nfused/N-confused sapphyrins, [51][52][53][54] and meso-tetraaryl-substituted sapphyrins. [55]…”

Section: Introductionmentioning

confidence: 99%

“…A large number of studies have characterized different sapphyrin derivatives, including β‐alkylated sapphyrins, core‐modified sapphyrins with heteroatoms (O, S, or Se), N‐fused/N‐confused sapphyrins, and meso ‐tetraaryl‐substituted sapphyrins . Sapphyrins containing four meso ‐aryl substituents can serve as favorable building blocks for the further design of molecules, which are similar to meso ‐aryl‐substituted porphyrins, whose redox properties and chemical reactions can be finely tuned .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Electrochemistry of Open‐Chain Pentapyrroles and Sapphyrins with Highly Electron‐Withdrawing meso‐Tetraaryl Substituents

Shan

Desbois

Blondeau-Pâtissier

et al. 2017

Chemistry A European J

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A series of open-chain pentapyrroles and sapphyrins with highly electron-withdrawing substituents (i.e., CN, CF , or CO Me) on the meso-phenyl rings was synthesized and characterized as to the spectral properties, protonation reactions, and electrochemistry in non-aqueous media. The investigated compounds are represented as (Ar) PPyH and (Ar) SapH where PPy and Sap correspond to the tri-anion of the open-chain pentapyrrole and sapphyrin, respectively, and Ar=p-CNPh, p-CF Ph, or p-CO MePh. UV/Vis and H NMR spectroscopy as well as mass spectrometry data are given for the confirmation of the structures for the newly synthesized compounds. An X-ray structure for one of the pentapyrroles, that is, (p-CF Ph) PPyH (2), is also presented. The protonation processes were examined by UV/Vis absorption spectroscopy during the titration of the compounds with trifluoroacetic acid (TFA) in CH Cl . Equilibrium constants for the protonation reactions were calculated by using both the Hill equation and the mole ratio method. The protonation-initiated conversion of pentapyrroles to sapphyrins upon oxidation was also investigated. Cyclic voltammetry was used to measure the redox potentials in CH Cl , PhCN, and/or pyridine (Py). Electrochemical properties, protonation constants, and chemical reactions of the six compounds in the two series were then analyzed as a function of the solvent properties and the type of the electron-withdrawing groups on the meso-phenyl rings.

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“…It was our expectation that the reaction between sapphyrin 8 and DMAD would lead to the formation of the D-A adduct 9 (or its dehydrogenatedd erivative 10)( Scheme 2), thus providing an ew route to benzodipyrrole-containing sapphyrins that would be complementary to that reported by Lee and coworkers. [37] However,this expectation was not realized.…”

Section: Resultsmentioning

confidence: 99%

Unprecedented Double aza‐Michael Addition within a Sapphyrin Core

Figueira

Marques

Farinha

et al. 2016

Chemistry A European J

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A novel sapphyrin derivative was obtained from the reaction between a free-base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza-Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N'-dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N-atoms are linked to the two sp(3) carbon atoms derived from a substituted acetylene.

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A Benzodipyrrole‐Derived Sapphyrin

Cited by 57 publications

References 24 publications

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

Synthesis, Characterization, and Electrochemistry of Open‐Chain Pentapyrroles and Sapphyrins with Highly Electron‐Withdrawing meso‐Tetraaryl Substituents

Unprecedented Double aza‐Michael Addition within a Sapphyrin Core

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