Although a wide variety of boron-based "scorpionate" ligands have been implemented, a modular route that offers facile access to different substitution patterns at boron has yet to be developed. Here, we demonstrate new reactivity patterns at the bridgehead positions of a ruthenium tris(pyrid-2-yl)borate complex that allow for facile tuning of steric and electronic properties.
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http://dx.doi.org/10.1039/d1cc06181j | DOI Listing |
ACS Chem Biol
January 2025
Division of Physiological Chemistry and Metabolism, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-0011, Japan.
Macrophages remove apoptotic cells via phagocytosis, also known as efferocytosis, during inflammation to maintain tissue homeostasis. This process is accompanied by various metabolic changes in macrophages including the production of lipid metabolites by fatty acid oxygenases. Among these, highly reactive metabolites, called lipid-derived electrophiles (LDEs), modify cysteines and other nucleophilic amino acids in intracellular proteins.
View Article and Find Full Text PDFNature
January 2025
Manchester Institute of Biotechnology, The University of Manchester, Manchester, UK.
Nucleophilic aromatic substitutions (SAr) are amongst the most widely used processes in the pharmaceutical and agrochemical industries, allowing convergent assembly of complex molecules through C-C and C-X (X = O, N, S) bond formation. SAr reactions are typically carried out using forcing conditions, involving polar aprotic solvents, stoichiometric bases and elevated temperatures, which do not allow for control over reaction selectivity. Despite the importance of SAr chemistry, there are only a handful of selective catalytic methods reported that rely on small organic hydrogen-bonding or phase-transfer catalysts.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Department of Chemistry, Faculty of Arts and Sciences, Amasya University, Amasya, Turkey.
Herein, a new metal-free, molecular chlorine-free, environmentally friendly, atom-economical, short time, inexpensive and simple operation method with mild reaction conditions for chlorination of alkenes, cyclic alkenes, ,-unsaturated carbonyl compounds, heteroaromatics, and natural products was reported with up to 96% yields using trichloroisocyanuric acid (TCCA) as the electrophilic chlorine source and TBACl as the nucleophilic chlorine source. It was demonstrated with bicyclic alkene benzonorbornadiene that regioselective chlorobromination and dibromination reactions can be carried out through TCCA/TBABr redox reactions, where TCCA acts as an oxidant in the presence of TBABr. The structures of the redox products were confirmed as a result of control experiments conducted with the newly presented DBI/TBACl and DBI/TBABr halogenation pairs.
View Article and Find Full Text PDFChemphyschem
January 2025
University of Namur, Department of Chemistry, Rue de Bruxelles, 61, 5000, Namur, BELGIUM.
The [4+2] Diels-Alder cycloaddition reaction between 2,5-DMF (1) and ethylene derivatives (2a-h) activated by electron-withdrawing groups has been studied at the density functional theory levels using a panoply of tools to unravel the reaction mechanisms. From the analysis of the reactivity indices, 2a-h behave as electrophiles while 1 as nucleophile, and the activation of the double bond of ethylene increases its electrophilicity, which is accompanied by an enhancement of the polarity of the reaction. The activation Gibbs free energy decreases linearly as a function of this increase of polarity, as estimated by the electrophilicity difference between the reactants.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Institute of Materia Medica Chinese Academy of Sciences, Chemical Biology Research Center, 201203, Shanghai, CHINA.
Aldolases are powerful C-C bond-forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. This study documented the semirational engineering of the decarboxylative aldolase UstD with the focused rational iterative site-specific mutagenesis (FRISM) strategy to perform a C-C bond-forming reaction with dione electrophiles.
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