Corrole

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:{{cite journal | doi=10.1021/acs.chemrev.6b00434 | title=Synthesis of Corroles and Their Heteroanalogs | year=2017 | last1=Orłowski | first1=Rafał | last2=Gryko | first2=Dorota | last3=Gryko | first3=Daniel T. | journal=Chemical Reviews | volume=117 | issue=4 | pages=3102–3137 | pmid=27813401 }}

Image:Corrole revisedII.png

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.{{Cite journal|last1=Thomas|first1=Kolle E.|last2=Alemayehu|first2=Abraham B.|last3=Conradie|first3=Jeanet|last4=Beavers|first4=Christine M.|last5=Ghosh|first5=Abhik|date=2012-08-21|title=The Structural Chemistry of Metallocorroles: Combined X-ray Crystallography and Quantum Chemistry Studies Afford Unique Insights|journal=Accounts of Chemical Research|volume=45|issue=8|pages=1203–1214|doi=10.1021/ar200292d|pmid=22444488|issn=0001-4842}} 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:

Corroles have been attached to a wide range of transition metals,{{Cite journal|last=Ghosh|first=Abhik|date=2017-02-22|title=Electronic Structure of Corrole Derivatives: Insights from Molecular Structures, Spectroscopy, Electrochemistry, and Quantum Chemical Calculations|journal=Chemical Reviews|volume=117|issue=4|pages=3798–3881|doi=10.1021/acs.chemrev.6b00590|pmid=28191934|issn=0009-2665}} main group elements,{{cite journal | last1 = Aviv-Harel | first1 = I. | last2 = Gross | first2 = Z. | year = 2010 | title = Coordination chemistry of corroles with focus on main group elements| doi = 10.1016/j.ccr.2010.09.013 | journal = Coord. Chem. Rev. | volume = 255 | issue = 7–8| pages = 717–736 }} and lanthanides,{{cite journal | last1 = Buckley | first1 = H. L. | last2 = Anstey | first2 = M. R. | last3 = Gryko | first3 = D. T. | last4 = Arnold | first4 = J. | year = 2013 | title = Lanthanide corroles: a new class of macrocyclic lanthanide complexes| doi = 10.1039/c3cc38806a | pmid = 23467462 | journal = Chem. Commun. | volume = 49 | issue = 30| pages = 3104–3106 }} actinides.{{cite journal | last1 = Ward | first1 = A. L. | last2 = Buckley | first2 = H. L. | last3 = Lukens | first3 = W. W. | last4 = Arnold | first4 = J. | year = 2013 | title = Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes| journal = J. Am. Chem. Soc. | volume = 135 | issue = 37| pages = 13965–13971 | doi=10.1021/ja407203s | pmid=24004416}} and the diprotonated, neutral corrole radical.{{cite journal |vauthors=Schweyen P, Brandhorst K, Wicht R, Wolfram B, Bröring M |title=The Corrole Radical |journal=Angew. Chem. Int. Ed. |volume=54|issue=28 |pages=8213–8216 |date=2015 |pmid=26074281 |doi=10.1002/anie.201503624 }} Additionally, corroles and their metal complexes have been demonstrated to be useful as imaging agents in tumor detection,{{cite journal | doi=10.1021/acs.chemrev.6b00400| title=Fighting Cancer with Corroles| year=2017| last1=Teo| first1=Ruijie D.| last2=Hwang| first2=Jae Youn| last3=Termini| first3=John| last4=Gross| first4=Zeev| last5=Gray| first5=Harry B.| journal=Chemical Reviews| volume=117| issue=4| pages=2711–2729| pmid=27759377| pmc=6357784}} oxygen sensing,{{Cite journal|last1=Borisov|first1=Sergey M.|last2=Alemayehu|first2=Abraham|last3=Ghosh|first3=Abhik|title=Osmium-nitrido corroles as NIR indicators for oxygen sensors and triplet sensitizers for organic upconversion and singlet oxygen generation|journal=Journal of Materials Chemistry C|language=en|doi=10.1039/C6TC01126H|issn=2050-7534|volume=4|issue=24|pages=5822–5828|year=2016|doi-access=free|hdl=10037/24918|hdl-access=free}} for prevention of heart disease,{{cite journal | last1 = Haber | first1 = Adi | last2 = Ali | first2 = A. A.-Y. | last3 = Aviram | first3 = M. | last4 = Gross | first4 = Z. | year = 2013 | title = Allosteric inhibitors of HMG-CoA reductase, the key enzyme involved in cholesterol biosynthesis| doi = 10.1039/c3cc44740e | pmid = 23958894 | journal = Chem. Commun. | volume = 49 | issue = 93| pages = 10917–10919 }} in synthetic chemistry as oxo, imido, and nitrido transfer agents,{{cite book | last1 = Palmer | first1 = J. H. | title = Molecular Electronic Structures of Transition Metal Complexes I | year = 2012 | chapter = Transition Metal Corrole Coordination Chemistry| doi = 10.1007/430_2011_52| journal = Struct. Bond. | volume = 142 | pages = 49–90 | series = Structure and Bonding | isbn = 978-3-642-27369-8 }} and as catalysts for the catalytic reduction of oxygen to water,{{cite journal | last1 = Dogutan | first1 = D. K. | last2 = Stoian | first2 = S. A. | last3 = McGuire | first3 = R. | last4 = Schwalbe | first4 = M. | last5 = Teets | first5 = T. S. | last6 = Nocera | first6 = D. G. | year = 2011 | title = Hangman Corroles: Efficient Synthesis and Oxygen Reaction Chemistry| journal = J. Am. Chem. Soc. | volume = 133 | issue = 1| pages = 131–140 | doi=10.1021/ja108904s | pmid=21142043}} and hydrogen production form water under aerobic conditions.

Protein-corrole particles have been investigated as carriers of theranostic cargo for tumor targeting.{{cite book|first1=James | last1=Teh

|first2=Lali Medina|last2=Kauwe|title=Metal Ions in Bio-Imaging Techniques|publisher=Springer|year=2021|pages=299–314|chapter=Chapter 10. Magnetic Resonance Contrast Enhancement and Therapeutic Properties of Corrole Nanoparticles|doi=10.1515/9783110685701-016| s2cid=233677374

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Category:Chelating agents

Category:Tetrapyrroles

Category:Macrocycles