The reaction of Cu(ClO4)2. 6H2O with t-BuP(O)(OH)2 and 3,5-(CF3)2PzH in the presence of triethylamine afforded the dodecanuclear cage ([Et3NH]2[Cu12(mu-3,5-(CF3)2Pz)6(mu3-OH)6(mu-OH)3(mu3-t-BuPO3)2(mu6-t-BuPO3)3][t-BuPO2OH][C6H5CH3]2) (2). The molecular structure of this cage revealed that it possesses a barrel-shaped architechture. The cage structure is built by the cumulative coordination action of phosphonate, hydroxide, and pyrazolyl ligands. A similar reaction involving Cu(NO3)2. 3H2O, t-BuP(O)(OH)2, 3,5-dimethylpyrazole, and triethylamine afforded another dodecanuclear cage [Cu12(mu-DMPz)8(eta1-DMPzH)2(mu4-O)2(mu3-OH)4(mu3- t-BuPO3)4].3MeOH (3). The latter is crown-shaped and is built by the coordination of pyrazole, pyrazolyl, phosphonate, hydroxide, oxide, and methanol ligands. Both of the dodecanuclear cages are efficient nucleases in the presence of magnesium monoperoxyphthalate.
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http://dx.doi.org/10.1021/ic800509f | DOI Listing |
Chem Commun (Camb)
January 2025
Department of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500007, India.
Herein, we have developed a Pd(II)-catalyzed cyclization of prochiral alkyne-tethered malononitriles to access five-membered carbocycles having a nitrile-containing all-carbon quaternary center. The reaction pathway involves a -acetoxypalladation, nitrile group insertions into the carbon-palladium bond and sequential deacetylation followed by -acetylation. Initial studies on asymmetric cyclization were also performed with chiral Pyox ligands.
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January 2025
Department of Chemistry, University at Albany, State University of New York Albany New York 12222 USA
The chemical reduction of a pyracylene-hexa--hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added to its π-system.
View Article and Find Full Text PDFACS Catal
January 2025
Fakultät für Chemie und Pharmazie, Universität Regensburg, Regensburg 93040, Germany.
Transition metal catalysis is crucial for the synthesis of complex molecules, with ligands and bases playing a pivotal role in optimizing cross-coupling reactions. Despite advancements in ligand design and base selection, achieving effective synergy between these components remains challenging. We present here a general approach to nickel-catalyzed photoredox reactions employing -butylamine as a cost-effective bifunctional additive, acting as the base and ligand.
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January 2025
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, United Kingdom.
An aryl radical assay is used to provide information about the formation of aryl radicals from aryl halides in coupling reactions to arenes in the presence of palladium sources and under LED irradiation (λ = 456 nm). The assay uses 2-halo--xylenes as substrates. Aryl radical formation is indicated both by a defined product composition and by signature deuterium isotope effects.
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January 2025
Chemical Biotechnology, Groningen Biomolecular Sciences and Biotechnology Institute (GBB), University of Groningen, 9747 AG Groningen, the Netherlands.
Aspartate ammonia lyases catalyze the reversible amination of fumarate to l-aspartate. Recent studies demonstrate that the thermostable enzyme from sp. YM55-1 (AspB) can be engineered for the enantioselective production of substituted β-amino acids.
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