A chiral metallocorrole complex, oxo[5-(4-bromophenyl)-10-(pentafluorophenyl)-15-(2-thianaphthyl)corrolato]chromium(V) (7), was prepared and serves as the first example of an ABC-metallocorrole; meso substituents are of different electron-withdrawing capacity. An adaptation of a multistep protocol (D. T. Gryko) was made, followed by an aerobic oxidation using Cr(CO)(6) (Z. Gross). The X-ray crystal structure reveals the two enantiomers of 7. Electron paramagnetic resonance spectroscopy (g(iso) = 1.99) and cyclic voltammetry of 7 provide comparative data to that of the A(3)[tris(pfp)cCr(V)O] complex.
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http://dx.doi.org/10.1021/ic900393v | DOI Listing |
J Am Chem Soc
January 2025
BioCIS, Faculté de Pharmacie, Université Paris-Saclay, CNRS, Orsay 91400, France.
The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China.
-cycloalkenes are abundant in bioactive natural products and have been used as powerful tools in chemical biology and drug discovery. However, strategies for the modular synthesis of -cycloalkenes, especially planar-chiral medium-sized ones, with high efficiency and selectivity, still remain elusive. Herein, we report a Pd-catalyzed asymmetric [7 + 2] cyclization strategy to address this challenge.
View Article and Find Full Text PDFNano Lett
January 2025
Zhejiang Engineering Research Center for Tissue Repair Materials and Wenzhou Key Laboratory of Biomaterials and Engineering and Wenzhou Key Laboratory of Biophysics, Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou 325001, China.
Saccharides and peptides with markedly disparate stereochemical features serve as pivotal chiral molecular partners in living systems. The importance of glycosylation in influencing glycopeptide self-assembly has been recognized. However, how different chiral combinations of saccharides and peptides influence the macroscopic hydrogel mechanics, fiber nanomechanics, asymmetric molecular packing, and thermodynamic changes during glycopeptide self-assembly remains unknown.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Basel, Department of Chemistry, St. Johanns-Ring 19, 4056, Basel, SWITZERLAND.
Despite the growing importance of planar chiral macrocyclophanes owing to their unique properties in different areas of chemistry, methods that are effective in controlling their planar chirality are restricted to certain molecular scaffolds. Herein, we report the first Pd(0)-catalyzed enantioselective intermolecular C-H arylation that induces planar chirality by installing bulky aryl groups through dynamic kinetic resolution (DKR). A computer-assisted approach allowed a fine-tuning of the structure of the employed chiral bifunctional phosphine-carboxylate ligands to achieve high enantioselectivities.
View Article and Find Full Text PDFPest Manag Sci
January 2025
Heinrich-Heine-University Düsseldorf, Institute of Organic Chemistry and Macromolecular Chemistry, Duesseldorf, Germany.
Chemical crop protection is one of the most cost-effective methods for agriculture, as crop failures can be prevented, and sustainable growth can be enabled regardless of the seasons. Agricultural production must be significantly increased in the future to meet the food needs of a growing world population. However, the continued loss of established active ingredients due to consumer perceptions, changing needs of farmers and ever-changing regulatory requirements is higher than annually new active ingredients introduced to the market.
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