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The unique structure of oxyallyls represents a significant challenge for their catalytic asymmetric applications. Herein, an unprecedented chiral imidodiphosphoric acid-catalytic enantioselective (3 + 3) cycloaddition between oxyallyl zwitterions generated from α-haloketones and α-diazomethylphosphonates was developed. Pharmaceutically interesting chiral pyridazine-4()-ones were obtained in up to 98% yields with excellent stereoselectivities (up to 99% ee, > 99:1 dr).
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http://dx.doi.org/10.1021/acs.orglett.1c02809 | DOI Listing |
Org Biomol Chem
September 2025
MOE Key Laboratory of Functional Molecular Solids, Anhui Laboratory of Molecule-Based Materials, Institute of Organic Chemistry, College of Chemistry and Materials Science, Anhui Normal University, 189 South Jiuhua Road, Wuhu, Anhui 241002, China.
The enantioselective kinetic resolution of racemic 2-ethynylaziridines ring opening with amines is realized under the catalysis of a chiral Cu(I)-bisphosphine combination. This protocol provides an expedient way to access synthetically valuable enantioenriched propargylic vicinal diamines (70%-95% yields, 14%-95% ee) and 2-ethynylaziridines (70%-95% recovery rates, 14%-95% ee) within 15-240 h under mild reaction conditions.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
The carbonyl-ene reaction between aldehydes and olefins constitutes a perfectly atom economic approach to homoallylic alcohols with concomitant C-C bond formation. However, the scope of catalytic asymmetric intermolecular versions is currently limited to activated substrates, while of the two intramolecular types only catalytic asymmetric (-)-carbonyl-ene type cyclizations can be considered mature. The corresponding (-)-cyclizations would arguably find equal utility in chemical synthesis but remain underdeveloped.
View Article and Find Full Text PDFJ Phys Chem A
September 2025
Department of Chemistry, Tsinghua University, Beijing 100084, China.
A series of Cu-based single-atom catalysts (SACs) with asymmetric coordination were designed to accelerate lithium-sulfur (Li-S) chemistry. The electronegativity contrast from the dopant induces a localized electronic asymmetry that amplifies Jahn-Teller distortion at the Cu center. This distortion profoundly modulates the Cu 3d electronic structure and its interaction with Li-S intermediates.
View Article and Find Full Text PDFACS Nano
September 2025
CINBIO and Departamento de Química Orgánica. Campus Lagoas-Marcosende, Universidade de Vigo, Vigo E-36310, Spain.
Archimedean spirals are architectural motifs that are found in nature. The facial asymmetry of amphiphilic molecules or macromolecules has been a key parameter in the preparation of these well-organized two-dimensional nanostructures in the laboratory. This facial asymmetry is also present in the helical grooves of chiral helical substituted poly(phenylacetylene)s (PPAs) and poly(diphenylacetylene)s (PDPAs), making them excellent candidates for self-assembly into 2D Archimedean nanospirals or nanotoroids.
View Article and Find Full Text PDFSmall
September 2025
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan, 250014, P. R. China.
The functionality of covalent organic frameworks (COFs) is usually highly related to their morphologies. Among various morphologies, the hollow-structured COFs have recently attracted intense attention due to their unique properties. Herein, the synthesis of hollow structured COFs are first reported with the chiral internal sites via combining the chiral templating method with the acid etching approach.
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