The Total Synthesis of Pyrrole Pigments

Jackson, Anthony H.

doi:10.1002/9780470129647.ch3

Cited by 12 publications

(2 citation statements)

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“…A multitude of preparative routes to monopyrroles exist; reviews of this literature have been published [1, 15-17]. Methods for elaboration of monopyrroles into dipyrromethane, tripyrrane, and a,c-biladiene compounds will be discussed in the sections related to the porphyrins in which they are used as essential intermediates.…”

Section: Porphyrin Synthesesmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

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Porphyrin macrocycles have been the subject of intense study in the last century because they are widely distributed in nature, usually as metal complexes of either iron or magnesium. As such, they serve as the prosthetic groups in a wide variety of primary metabolites, such as hemoglobins, myoglobins, cytochromes, catalases, peroxidases, chlorophylls, and bacteriochlorophylls; these compounds have multiple applications in materials science, biology and medicine. This article describes current methodology for preparation of simple, symmetrical model porphyrins, as well as more complex protocols for preparation of unsymmetrically substituted porphyrin macrocycles similar to those found in nature. The basic chemical reactivity of porphyrins and metalloporphyrin is also described, including electrophilic and nucleophilic reactions, oxidations, reductions, and metal-mediated cross-coupling reactions. Using the synthetic approaches and reactivity profiles presented, eventually almost any substituted porphyrin system can be prepared for applications in a variety of areas, including in catalysis, electron transport, model biological systems and therapeutics.

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Section: Porphyrin Synthesesmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

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“…35 Five-membered heterocyclic pyrroles and their derivatives have attracted broad interest because of their presence in many biologically important molecules. 36,37 The pyrrole derivative, 2cyanopyrrole, with a CN group in the α-position, is an important intermediate in the synthesis of porphyrins. 38 The 2-CNPyr − anion is widely used in ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

Dipole-Bound State, Photodetachment Spectroscopy, and Resonant Photoelectron Imaging of Cryogenically-Cooled 2-Cyanopyrrolide

2022

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Valence-bound anions with polar neutral cores can have diffuse dipole-bound excited states just below the electron detachment threshold. Because of the similarity in geometry and vibrational frequencies between the dipole-bound states (DBSs) and the corresponding neutrals, DBSs have been exploited as intermediate states to conduct resonant photoelectron spectroscopy (PES), resulting in highly non-Franck−Condon photoelectron spectra via vibrational autodetachment and providing much richer vibrational information than conventional PES. Here, we report a photodetachment and high-resolution photoelectron imaging study of the 2-cyanopyrrolide anion, cooled in a cryogenic ion trap. The electron affinity of the 2-cyanopyrrolyl radical is measured to be 3.0981 ± 0.0006 eV (24 988 ± 5 cm −1 ). A DBS is observed for 2cyanopyrrolide at 240 cm −1 below its detachment threshold using photodetachment spectroscopy. Twenty-three above-threshold vibrational resonances (Feshbach resonances) of the DBS are observed. Resonant PES is conducted at each Feshbach resonance, yielding a wealth of vibrational information about the 2-cyanopyrrolyl radical. Resonant two-photon PES confirms the s-like dipolebound orbital and reveals a relatively long lifetime of the bound zero-point level of the DBS. Fundamental frequencies for 19 vibrational modes (out of a total of 24) are obtained for the cyanopyrrolyl radical, including six out-of-plane modes. The current work provides important spectroscopic information about 2-cyanopyrrolyl, which should be valuable for the study of this radical in combustion or astronomical environments.

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