A catalyst bound α-aminoalkyl radical intermediate from iminium is developed to control its formation and reactivity with aerobic oxygen. The influence of the catalyst was demonstrated via the ease of radical intermediate formation and its subsequent reactivity, including the first catalyst-controlled enantioselective aerobic oxidation with a chiral phosphite catalyst.
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http://dx.doi.org/10.1039/c8ob01032c | DOI Listing |
Environ Sci Pollut Res Int
January 2025
Centre de Recherche Scientifique Et Technique en Analyses Physico-Chimiques, CP 42004, Bou-Ismail, Tipaza, Algeria.
ZnO-CoO material was successfully synthesized by the co-precipitation method and used as a catalyst for the removal of diclofenac sodium (DCF). ZnO-CoO exhibited higher catalytic activity in the catalytic process compared to the photocatalytic processes. Under optimum conditions, the activation of peroxymonosulfate (PMS) by ZnO-CoO achieved approximately 99% removal of DCF, confirming the effective adsorption and activation of PMS.
View Article and Find Full Text PDFJ Mol Model
January 2025
Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, 7820436, Santiago de Chile, Chile.
Context: Dopamine -monooxygenase (D M) is an essential enzyme in the organism that regioselectively converts dopamine into R-norepinephrine, the key step of the reaction, studied in this paper, is a hydrogen atom transfer (HAT) from dopamine to a superoxo complex on D M, forming a hydroperoxo intermediate and dopamine radical. It was found that the formation of a hydrogen bond between dopamine and the D M catalyst strengthens the substrate-enzyme interaction and facilitates the HAT which takes place selectively to give the desired enantiomeric form of the product. Six reactions leading to the hydroperoxo intermediate were analyzed in detail using theoretical and computational tools in order to identify the most probable reaction mechanism.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.
View Article and Find Full Text PDFCancer
January 2025
Department of Urology, Cedars-Sinai Medical Center, Los Angeles, California, USA.
Background: Adverse pathology (AP) is often used as an intermediate end point for long-term outcomes in men with prostate cancer (PCa) who are active surveillance candidates. The association between a commonly used AP definition and long-term outcomes was tested, which identified definitions more strongly linked to a high risk of metastasis.
Methods: Data were reviewed from the Shared Equal Access Regional Cancer Hospital cohort of men undergoing radical prostatectomy (RP) from 1988 to 2020 at nine Veterans Affairs hospitals.
J Am Chem Soc
January 2025
Key Laboratory of Chemical Biology of Fujian Province, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates.
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