620-08-6Relevant articles and documents
A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
supporting information, (2022/01/04)
The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
Selective and Efficient Photoinactivation of Intracellular Staphylococcus aureus and MRSA with Little Accumulation of Drug Resistance: Application of a Ru(II) Complex with Photolabile Ligands
Sun, Weize,Jian, Yao,Zhou, Mengxue,Yao, Yishan,Tian, Na,Li, Chao,Chen, Jun,Wang, Xuesong,Zhou, Qianxiong
supporting information, p. 7359 - 7370 (2021/06/21)
Novel antibacterial agents capable of efficiently sterilizing intracellular Staphylococcus aureus and methicillin-resistant S. aureus (MRSA) but with low cytotoxicity and low resistance development are quite appealing. In this work, three Ru(II) complexes with photolabile ligands were explored to realize such a goal. Complex 3 (5 μM) can inhibit more than 90% growth of S. aureus/MRSA that has invaded in J774A.1 cells upon visible light irradiation, being much more efficient than vancomycin. In similar conditions, negligible dark- and phototoxicity were found toward the host cells. The bactericidal activity is highly correlated with DNA covalent binding by the Ru(II) fractions generated after ligand photodissociation. Moreover, S. aureus quickly developed resistance toward vancomycin, while negligible resistance toward complex 3 even after 700 generations was obtained. These appealing results may pave a new way for fighting against intracellular antibiotic-resistant pathogens.
Photocatalytic deoxygenation of N-O bonds with rhenium complexes: From the reduction of nitrous oxide to pyridineN-oxides
Anthore-Dalion, Lucile,Cantat, Thibault,Kjellberg, Marianne,Nicolas, Emmanuel,Ohleier, Alexia,Thuéry, Pierre
, p. 10266 - 10272 (2021/08/12)
The accumulation of nitrogen oxides in the environment calls for new pathways to interconvert the various oxidation states of nitrogen, and especially their reduction. However, the large spectrum of reduction potentials covered by nitrogen oxides makes it difficult to find general systems capable of efficiently reducing variousN-oxides. Here, photocatalysis unlocks high energy species able both to circumvent the inherent low reactivity of the greenhouse gas and oxidant N2O (E0(N2O/N2) = +1.77 Vvs.SHE), and to reduce pyridineN-oxides (E1/2(pyridineN-oxide/pyridine) = ?1.04 Vvs.SHE). The rhenium complex [Re(4,4′-tBu-bpy)(CO)3Cl] proved to be efficient in performing both reactions under ambient conditions, enabling the deoxygenation of N2O as well as synthetically relevant and functionalized pyridineN-oxides.
