A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni /Ni pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
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http://dx.doi.org/10.1002/anie.201910436 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Sichuan University, State Key Laboratory of Biotherapy, CHINA.
Herein we report a cobalt-catalyzed hydroglycosylation of terminal alkynes, employing bench-stable ortho-iodobiphenyl (oIB) substituted sulfides as glycosyl donors. This reaction occurs with high stereo- and regioselectivity to afford E-configured vinyl α-C-glycosides, a class of compounds nontrivial to access by previous methods. The use of a bis(oxazoline) ligand with bulky side chains is critical for the high selectivities observed.
View Article and Find Full Text PDFActa Pharm Sin B
December 2024
Rehabilitation Medicine Center and Institute of Rehabilitation Medicine, Cancer Center and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, China.
Reactive oxygen species (ROS)-responsive drug delivery systems (DDSs) have garnered significant attention in cancer research because of their potential for precise spatiotemporal drug release tailored to high ROS levels within tumors. Despite the challenges posed by ROS distribution heterogeneity and endogenous supply constraints, this review highlights the strategic alliance of ROS-responsive DDSs with photodynamic therapy (PDT), enabling selective drug delivery and leveraging PDT-induced ROS for enhanced therapeutic efficacy. This review delves into the biological importance of ROS in cancer progression and treatment.
View Article and Find Full Text PDFDalton Trans
January 2025
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR 6302 CNRS, Université de Bourgogne, 9 Avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France.
Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.
View Article and Find Full Text PDFJ Org Chem
January 2025
Institute of Materia Medica, School of Pharmaceutical Sciences, Nanjing Tech University, Nanjing 211816, P. R. China.
In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to the synthesis of polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles by eliminating the reliance on transition metals, external oxidants, and photocatalysts. The broad applicability of our method is demonstrated through the successful synthesis of a diverse array of compounds, including vinyl sulfones, vinyl selenides, and vinyl sulfides.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, People's Republic of China.
Metal-catalytic conversion of polysulfide reagents is a major challenge in organic synthesis due to its challenging activation modes of multiple S-S bonds. The utilization of aryl di- and trithiosulfonates in nickel-catalyzed reductive coupling with aryl halides has been unexplored. Herein, we unprecedentedly describe PPh and Zn-collaborative reduction-induced nickel-catalytic selective C-S coupling of aryl di/trithiosulfonates with aryl halides to access sulfides over common disulfides or trisulfides.
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