Corrole

Cobalamin structure includes a deprotonated corrin macrocycle.

A corrole is an aromatic tetrapyrrole. The corrin ring is also present in cobalamin (vitamin B₁₂). The ring consists of nineteen carbon atoms, with four nitrogen atoms in the core of the molecule. In this sense, corrole is very similar to porphyrin.

Preparation

Corroles can be prepared by a two-step process, beginning with the condensation reaction of a benzaldehyde with pyrrole. The open-ring product, a bilane (or tetrapyrrane), is cyclized by oxidation, typically with p-chloranil: ^[1]

Corrole synthesis

Comparison with porphyrins

Corrole and porphyrins differ in several ways. Corroles are triprotic, whereas porphyrins are diprotic. Because of the 3- charge of the triply deprotonated ligand, metallocorroles are formally high-valent. Several are redox-noninnocent, with a corrole radical-dianion ligand. ^[2] A second difference between corroles and porphyrins is the size of the metal-binding cavity, i.e., 17- vs 18-membered rings. See "Porphyrins and similar compounds" in conjugated systems for more about these side by side images of porphyrin, chlorin, and corrin structures. Due to their lower symmetry, corroles display broader Soret or B-bands and relatively stronger Q-bands, compared to porphyrins. The absorption spectra of corroles in the UV/Visible range tends to be more sensitive towards substituents than in the case of porphyrins.

Coordination complexes

Corroles have been attached to a wide range of transition metals, ^{[1] [3]} main group elements, ^[4] and lanthanides, ^[5] actinides. ^[6] and the diprotonated, neutral corrole radical. ^[7] Additionally, corroles and their metal complexes have been demonstrated to be useful as imaging agents in tumor detection, ^[8] oxygen sensing, ^[9] for prevention of heart disease, ^[10] in synthetic chemistry as oxo, imido, and nitrido transfer agents, ^[11] and as catalysts for the catalytic reduction of oxygen to water, ^[12] and hydrogen production form water under aerobic conditions.

Protein-corrole particles have been investigated as carriers of theranostic cargo for tumor targeting. ^[13]

References

1. Orłowski, Rafał; Gryko, Dorota; Gryko, Daniel T. (2017). "Synthesis of Corroles and Their Heteroanalogs". Chemical Reviews. 117 (4): 3102–3137. doi:10.1021/acs.chemrev.6b00434. PMID   27813401.
2. Thomas, Kolle E.; Alemayehu, Abraham B.; Conradie, Jeanet; Beavers, Christine M.; Ghosh, Abhik (2012-08-21). "The Structural Chemistry of Metallocorroles: Combined X-ray Crystallography and Quantum Chemistry Studies Afford Unique Insights". Accounts of Chemical Research. 45 (8): 1203–1214. doi:10.1021/ar200292d. ISSN   0001-4842. PMID   22444488.
3. Ghosh, Abhik (2017-02-22). "Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations". Chemical Reviews. 117 (4): 3798–3881. doi:10.1021/acs.chemrev.6b00590. ISSN   0009-2665. PMID   28191934.
4. Aviv-Harel, I.; Gross, Z. (2010). "Coordination chemistry of corroles with focus on main group elements". Coord. Chem. Rev. 255 (7–8): 717–736. doi:10.1016/j.ccr.2010.09.013.
5. Buckley, H. L.; Anstey, M. R.; Gryko, D. T.; Arnold, J. (2013). "Lanthanide corroles: a new class of macrocyclic lanthanide complexes". Chem. Commun. 49 (30): 3104–3106. doi:10.1039/c3cc38806a. PMID   23467462.
6. Ward, A. L.; Buckley, H. L.; Lukens, W. W.; Arnold, J. (2013). "Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes". J. Am. Chem. Soc. 135 (37): 13965–13971. doi:10.1021/ja407203s. PMID   24004416.
7. Schweyen P, Brandhorst K, Wicht R, Wolfram B, Bröring M (2015). "The Corrole Radical". Angew. Chem. Int. Ed. 54 (28): 8213–8216. doi:10.1002/anie.201503624. PMID   26074281.
8. Teo, Ruijie D.; Hwang, Jae Youn; Termini, John; Gross, Zeev; Gray, Harry B. (2017). "Fighting Cancer with Corroles". Chemical Reviews. 117 (4): 2711–2729. doi:10.1021/acs.chemrev.6b00400. PMC   6357784 . PMID   27759377.
9. Borisov, Sergey M.; Alemayehu, Abraham; Ghosh, Abhik (2016). "Osmium-nitrido corroles as NIR indicators for oxygen sensors and triplet sensitizers for organic upconversion and singlet oxygen generation". Journal of Materials Chemistry C. 4 (24): 5822–5828. doi: 10.1039/C6TC01126H . hdl: 10037/24918 . ISSN   2050-7534.
10. Haber, Adi; Ali, A. A.-Y.; Aviram, M.; Gross, Z. (2013). "Allosteric inhibitors of HMG-CoA reductase, the key enzyme involved in cholesterol biosynthesis". Chem. Commun. 49 (93): 10917–10919. doi:10.1039/c3cc44740e. PMID   23958894.
11. Palmer, J. H. (2012). "Transition Metal Corrole Coordination Chemistry". Molecular Electronic Structures of Transition Metal Complexes I. Structure and Bonding. Vol. 142. pp. 49–90. doi:10.1007/430_2011_52. ISBN   978-3-642-27369-8.{{cite book}}: |journal= ignored (help)
12. Dogutan, D. K.; Stoian, S. A.; McGuire, R.; Schwalbe, M.; Teets, T. S.; Nocera, D. G. (2011). "Hangman Corroles: Efficient Synthesis and Oxygen Reaction Chemistry". J. Am. Chem. Soc. 133 (1): 131–140. doi:10.1021/ja108904s. PMID   21142043.
13. Teh, James; Kauwe, Lali Medina (2021). "Chapter 10. Magnetic Resonance Contrast Enhancement and Therapeutic Properties of Corrole Nanoparticles". Metal Ions in Bio-Imaging Techniques. Springer. pp. 299–314. doi:10.1515/9783110685701-016. S2CID   233677374.