Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

• yielded minimal to no product. Among all the catalysts, corrole 99 turned out to be particularly effective in C–H-arylations, demonstrating high tolerance for various functional groups and higher product yields under both blue and sunlight. The authors suggested a radical mechanism similar to that of

• radical anion [67]˙− to give [67-H], the following reduction leads to thermodynamically favored [67-H]−, which then undergoes protonation and yields [67-HH]. In the last step, [67-HH] produces H2, and closes the catalytic cycle. Later, a different type of a metal-free tetrapyrrolic macrocycle, corrole

• activity in electrocatalytic HER [123]. Although free base corrole ligands demonstrated activity in HER, they were unstable in trifluoroacetic acid (TFA), a common proton source, leading to rapid degradation during catalysis. Subsequently, the same group introduced metal-free xanthene-bridged biscorroles

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

CuAAC-inspired synthesis of 1,2,3-triazole-bridged porphyrin conjugates: an overview

• Dileep Kumar Singh

Beilstein J. Org. Chem. 2023, 19, 349–379, doi:10.3762/bjoc.19.29

• photovoltaic device performance of porphyrins 53 and 57 was increased by eight-fold and four-fold, respectively, as compared to reference compounds without a triazole ring. Likewise, Nikolaou et al. [37] used zinc porphyrin 58 and copper-corrole 59 to synthesize first porphyrin-corrole dyad 60 through click

• protocol in a 42% yield by using CuI and DIPEA in THF at room temperature (Scheme 11). Their photophysical studies revealed that the fluorescence of zinc porphyrin 58 is strongly quenched due to the copper-corrole 59 in the dyad 60. Also, an efficient excited-state interaction was found between zinc

• -porphyrin and copper-corrole moieties upon photoexcitation. Moreover, the theoretical calculations suggested that the porphyrin moiety acted as a donor while the corrole unit acted as an acceptor in dimer 60. Recently S. Y. Yap and co-workers [38] used “click chemistry” to link a water-soluble porphyrin

Synthesis of meso-pyrrole-substituted corroles by condensation of 1,9-diformyldipyrromethanes with pyrrole

• Baris Temelli and
• Pinar Kapci

Beilstein J. Org. Chem. 2022, 18, 1403–1409, doi:10.3762/bjoc.18.145

• amount of pyrrole is presented for the first time. This procedure is a simple and efficient way for the preparation of corroles with a polymerizable substituent on meso-positions. Keywords: corrole; dipyrromethane; macrocycles; metal triflates; pyrrole; Introduction Corroles, a member of contracted

• devices and functional materials, the synthesis of corrole-based analogues has been rather limited due to very few synthetic methods developed to produce corroles with polymerizable substituents at the meso- or beta positions [10][11][12][13]. To date, meso-substituted corroles have been synthesized by

• our knowledge, there is no generally accepted method for the synthesis of pyrrole-substituted corroles. Very recently, we reported the synthesis of porphyrin–corrole [24][25][26] and porphyrin–porphyrin dyads and triads [27] using formylated porphyrin compounds. In a continuation of research activity

Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds

• Baris Temelli and
• Hilal Kalkan

Beilstein J. Org. Chem. 2018, 14, 187–193, doi:10.3762/bjoc.14.13

• Baris Temelli Hilal Kalkan Hacettepe University, Department of Chemistry, Beytepe Campus, 06800, Ankara, Turkey 10.3762/bjoc.14.13 Abstract The preparation of β-meso directly linked porphyrin–corrole hybrids was realized for the first time via an InCl3-catalyzed condensation reaction of 2-formyl

• -5,10,15,20-tetraphenylporphyrins with meso-substituted dipyrromethanes. Hybrid compounds have been characterized by 1H NMR, 13C NMR, 2D NMR, UV–vis absorption and fluorescence spectroscopy. Keywords: corrole; hybrid compounds; indium(III) chloride; porphyrin; porphyrinoids; Introduction Porphyrins and

• obtaining multiporphyrin arrays [7][8][9] that could stabilize only metal ions in a bivalent state. To overcome this limitation, porphyrin conjugates with different chromophore groups such as fullerene [10][11][12], BODIPY [13][14][15], corrole [16][17][18][19][20][21][22][23], phthalocyanine [24][25][26

Vinylphosphonium and 2-aminovinylphosphonium salts – preparation and applications in organic synthesis

• Anna Kuźnik,
• Roman Mazurkiewicz and
• Beata Fryczkowska

Beilstein J. Org. Chem. 2017, 13, 2710–2738, doi:10.3762/bjoc.13.269

• Gryko and Flamigni et al. for the preparation of 6-formylcoumarin derivatives 109 that are used in the synthesis of dyads 111 consisting of coumarin and corrole units (Scheme 61). The latter synthesis took place by condensation of formylcoumarins 109 with 5-(pentafluorophenyl)dipyrromethane (110) [76

Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

• Nicolas Desbois,
• Sandrine Pacquelet,
• Adrien Dubois,
• Clément Michelin and
• Claude P. Gros

Beilstein J. Org. Chem. 2015, 11, 2202–2208, doi:10.3762/bjoc.11.239

• ” reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were

• are promising contrast agents (CA) in MRI. Keywords: click chemistry; corrole; DOTA; microwave; NOTA; porphyrin; Introduction Magnetic resonance imaging (MRI), positron emission tomography (PET) or single photon emission computed tomography (SPECT) are actually the most commonly used imaging

• reported the successful synthesis of 64Cu-chelated porphyrin photosensitizers and a tumor targeting peptide. To the best of our knowledge, no previous example of the preparation of radioligand 64Cu corrole has been so far reported. Due to their easy copper insertion [21], corroles can be considered as