The photochemical oxidation of a (TAML)Fe complex using visible light generated Ru(bpy) produces valence tautomers (TAML)Fe ( ) and (TAML˙)Fe ( ), depending on the exogenous anions. The presence of labile Cl or Br results in a ligand-based oxidation and stabilisation of a radical-cationic (TAML˙)Fe complex, which subsequently leads to unprecedented C-H activation followed by nucleophilic substitution on the TAML aryl ring. In contrast, exogenous cyanide culminates in metal-based oxidation, yielding the first example of a crystallographically characterised = 1 [(TAML)Fe(CN)] species. This is a rare report of an anion-dependent valence tautomerisation in photochemically accessed high valent (TAML)Fe systems with potential applications in the oxidation of pollutants, hydrocarbons, and water. Furthermore, the nucleophilic aromatic halogenation reaction mediated by (TAML˙)Fe represents a novel domain for high-valent metal reactivity and highlights the possible intramolecular ligand or substrate modification pathways under highly oxidising conditions. Our findings therefore shine light on high-valent metal oxidants based on TAMLs and other potential non-innocent ligands and open new avenues for oxidation catalyst design.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5944818 | PMC |
| http://dx.doi.org/10.1039/c7sc05378a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Multi-Cancer Early Detection Tests: State of the Art and Implications for Radiologists.
Radiology
January 2025
From the Departments of Radiology and Population Health, New York University Langone Medical Center, New York, NY (S.K.K.); Division of Public Health Sciences, Fred Hutchinson Cancer Center, Seattle, Wash (R.G.); Department of Medicine, Vagelos College of Physicians and Surgeons, Columbia University, New York, NY (N.M., C.H.); Herbert Irving Comprehensive Cancer Center, New York, NY (C.H., E.B.E.); and Department of Health Policy and Management, Mailman School of Public Health, Columbia University, New York, NY (E.B.E.).
Multi-cancer early detection (MCED) tests are already being marketed as noninvasive, convenient opportunities to test for multiple cancer types with a single blood sample. The technology varies-involving detection of circulating tumor DNA, fragments of DNA, RNA, or proteins unique to each targeted cancer. The priorities and tradeoffs of reaching diagnostic resolution in the setting of possible false positives and negatives remain under active study.
View Article and Find Full Text PDFA deoxyfluoroalkylation-aromatization strategy to access fluoroalkyl arenes.
Chem Commun (Camb)
January 2025
Borch Department of Medicinal Chemistry, Purdue University, West Lafayette, IN, 47906, USA.
Fluoroalkyl arenes (Ar-R) are valuable substructures present in several FDA-approved drugs, patents, agrochemicals, and materials, and complementary strategies that enable access to a broad spectrum of Ar-R compounds benefit these applied fields. Herein, we report a deoxyfluoroalkylation-aromatization strategy to convert cyclohexanones into broad-spectrum Ar-R containing compounds. Generally, the fluoroalkyl sources were activated to participate in a 1,2-addition reaction followed by aromatization in a sequence that contrasts more common preparations of these Ar-R compounds, such as (i) transition-metal catalyzed cross-coupling reactions of aryl electrophiles and nucleophiles, and (ii) radical fluoroalkylation reactions of C-H bonds of arenes.
View Article and Find Full Text PDFRevealing the Monooxygenase Mechanism for Selective Ring Cleavage of Anthraquinone by BTG13 through Multiscale Simulations.
Chembiochem
January 2025
Renmin University of China, Chemistry, No.59 Zhongguangcun Street, Haidian District, 100872, Beijing, CHINA.
BTG13, a non-heme iron-dependent enzyme with a distinctive coordination environment of four histidines and a carboxylated lysine, has been found to catalyze the cleavage of the C4a-C10 bond in anthraquinone. Contrary to typical dioxygenase mechanisms, our quantum mechanical/molecular mechanical (QM/MM) calculations reveal that BTG13 functions more like a monooxygenase. It selectively inserts an oxygen atom into the C10-C4a bond, creating a lactone species that subsequently hydrolyzes, leading to the formation of a ring-opened product.
View Article and Find Full Text PDFUnderstanding the Reactivity of "Naked" Acyclic Carbene-like Species Featuring a Group 13 Element in the [4+1] Cycloaddition with Benzene.
Inorg Chem
January 2025
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
The chemical reactivity between benzene and the "naked" acyclic carbene-like (G13X) species, having two bulky N-heterocyclic boryloxy ligands at the Group 13 center, was theoretically assessed using density functional theory computations. Our theoretical studies show that (BX) preferentially undergoes C-H bond insertion with benzene, both kinetically and thermodynamically, whereas the (AlX) analogue favors a reversible [4 + 1] cycloaddition. Conversely, the heavier carbene analogues ((GaX), (InX), and (TlX)) are not expected to engage in a reaction with benzene.
View Article and Find Full Text PDFCatalytic Enantioselective Synthesis of Monosubstituted [n]Paracyclophane using a Desymmetrization/Kinetic Resolution Sequence.
Chemistry
January 2025
Beijing Normal University, College of Chemistry, Xiejiekou NO.19, 100875, Beijing, CHINA.
Optically pure monosubstituted [n]paracyclophanes are promising candidates for material synthesis, asymmetric catalysis, and drug discovery. Thus far, only a few catalytic asymmetric synthesis processes have been reported for assessing these stained atropisomers. In this study, we describe a highly enantioselective synthesis of monosubstituted [n]paracyclophanes by combining desymmetrization and kinetic resolution.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!