Propentdyopents [5-(2-oxo-2H-pyrrol-5-ylmethylene)pyrrol-2(5H)-ones] and related compounds. Part 1. On the structure of the propentdyopent–alkanol adducts

Bonnett, Raymond; Dimsdale, M. J.; Stephenson, G. F.

doi:10.1039/p19870000439

Cited by 11 publications

(9 citation statements)

References 6 publications

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“…Two different approaches for the synthesis of octaethyl‐10‐thiacorrole 1 have been devised: the MacDonald‐type [2+2] condensation of tetraethyl‐2,2′‐bipyrrole 2 18 and bis(3,4‐diethyl‐5‐formylpyrrole)sulfide 4 , and the copper(II)‐templated macrocyclization of dibromodipyrrin 5 19 in the presence of sodium sulfide,12d followed by reductive demetalation (Scheme ) 20. The former pathway produces the desired macrocycle in an acceptable 29 % yield in the final step.…”

Section: Resultsmentioning

confidence: 99%

Iron 10‐Thiacorroles: Bioinspired Iron(III) Complexes with an Intermediate Spin (S=3/2) Ground State

Sakow

Baabe

Böker

et al. 2014

Chemistry A European J

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A first systematic study upon the preparation and exploration of a series of iron 10-thiacorroles with simple halogenido (F, Cl, Br, I), pseudo-halogenido (N3 , I3 ) and solvent-derived axial ligands (DMSO, pyridine) is reported. The compounds were prepared from the free-base octaethyl-10-thiacorrole by iron insertion and subsequent ligand-exchange reactions. The small N4 cavity of the ring-contracted porphyrinoid results in an intermediate spin (i.s., S=3/2) state as the ground state for the iron(III) ion. In most of the investigated cases, the i.s. state is found unperturbed and independent of temperature, as determined by a combination of X-ray crystallography and magnetometry with (1) H NMR-, EPR-, and Mössbauer spectroscopy. Two exceptions were found. The fluorido iron(III) complex is inhomogenous in the solid and contains a thermal i.s. (S=3/2)→high spin (h.s., S=5/2) crossover fraction. On the other side, the cationic bis(pyridine) complex resides in the expected low spin (l.s., S=1/2) state. Chemically, the iron 10-thiacorroles differ from the iron porphyrins mainly by weaker axial ligand binding and by a cathodic shift of the redox potentials. These features make the 10-thiacorroles interesting ligands for future research on biomimetic catalysts and model systems for unusual heme protein active sites.

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Section: Resultsmentioning

confidence: 99%

Iron 10‐Thiacorroles: Bioinspired Iron(III) Complexes with an Intermediate Spin (S=3/2) Ground State

Sakow

Baabe

Böker

et al. 2014

Chemistry A European J

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“…The first example of the use of lead tetraacetate to oxidize pyrrolic species was carried out by Bonnet and co‐workers in 1987 . This involved the treatment of dipyrrole diacid 90 to give dipyrrolinone species 91 in a yield of 13 % (Scheme ).…”

Section: Miscellaneous Methods For the Oxidation Of Pyrrolementioning

confidence: 99%

The Oxidation of Pyrrole

Howard

Rihak

Bissember

et al. 2015

Chemistry An Asian Journal

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The dearomatization of heterocycles has been a powerful means for producing functional molecules in synthesis. In the case of pyrroles, reductive methods (such as the Birch reduction) have been most widely exploited, while oxidative methods are generally dismissed as too difficult or unpredictable to be useful. However, since the early twentieth century considerable research has been carried out on the controlled oxidation of pyrroles to give highly functionalized products, using a variety of oxidants. This review presents a summary of all work up until the present day in the area of pyrrole oxidation, looking at the use of peroxide, singlet oxygen, hypervalent iodine reagents, a range or organic and inorganic oxidants, and electrochemical approaches. It also offers some perspective on the potential future role of pyrrole oxidation in synthesis.

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“…We have shown that tetraethyl propentdyopent Hpdp coordinates divalent transition metals and that the resulting homoleptic pseudo‐tetrahedral complexes [M(pdp) 2 , Scheme ] host stable ligand‐based radicals upon one‐electron reduction . Although convenient syntheses of dipyrrindione ligands were first reported in the 1980s, their boron coordination has not been investigated to the best of our knowledge. Herein, we sought to combine the ability of the dipyrrindione moiety to act as a redox‐active ligand with the emission properties of BODIPY analogs to afford a novel redox‐switchable fluorophore.…”

Section: Introductionmentioning

confidence: 99%

Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

2018

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The combination of reversible redox chemistry and bright redox‐responsive emission properties is key to the development of electrofluorochromic switches for applications in bioimaging and optoelectronics. Herein, the redox‐active dipyrrin‐1,9‐dione fragment, which is characteristic of the propentdyopent family of heme metabolites and urinary pigments, is employed for the synthesis of a BODIPY analog. This boron difluoride complex exhibits bright fluorescence in organic solvents and a significant ipsochromic shift to the cyan region when compared to typical green BODIPY dyes. Electrochemical and spectroscopic measurements show that the dipyrrindione ligand acts as an electron reservoir by hosting an unpaired spin upon one‐electron reduction. This ligand‐based redox event reversibly abolishes the fluorescence emission, thus switching off the novel electrofluorochromic system.

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Propentdyopents [5-(2-oxo-2H-pyrrol-5-ylmethylene)pyrrol-2(5H)-ones] and related compounds. Part 1. On the structure of the propentdyopent–alkanol adducts

Abstract: First, the history of the structural problem of propentdyopents and their adducts (e.g.

Cited by 11 publications

References 6 publications

Iron 10‐Thiacorroles: Bioinspired Iron(III) Complexes with an Intermediate Spin (S=3/2) Ground State

Iron 10‐Thiacorroles: Bioinspired Iron(III) Complexes with an Intermediate Spin (S=3/2) Ground State

The Oxidation of Pyrrole

Redox‐Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments

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