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Synthesis and Reactivity of Six-Membered Cyclic Diaryl λ3-Bromanes and λ3-Chloranes.

Angew Chem Int Ed Engl

January 2025

Cardiff University, School of Chemistry, Park Place, Main Building, CF10 3AT, Cardiff, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.

Despite the remarkable advancements in hypervalent iodine chemistry, exploration of bromine and chlorine analogues remains in its infancy due to their difficult synthesis. Herein, we introduce six-membered cyclic λ3-bromanes and λ3-chloranes. Through single-crystal X-ray structural analyses and conformational studies, we delineate the crucial bonding patterns pivotal for the thermodynamic stability of these compounds.

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Reliable methods for rapidly constructing C(sp3)-rich three-dimensional polycycles are in high demand for organic synthesis and medicinal chemistry. Although there are various mature systems for synthesizing five- or six-membered polycycles, a catalytic platform for accessing diverse cycloheptanoid-containing polycyclic scaffolds is lacking. Herein, we describe a method for copper-catalyzed intramolecular 2-aminoallyl cation-diene (4 + 3) cycloaddition reactions.

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Zwitterionic polymers have garnered significant attention for their distinctive properties, such as biocompatibility, antifouling capabilities, and resistance to protein adsorption, making them promising candidates for a wide range of applications, including drug delivery, oil production inhibitors, and water purification membranes. This study reports the synthesis and characterization of zwitterionic monomers and polymers through the modification of linear, vinyl, and aromatic heterocyclic functional groups via reaction with 1,3-propanesultone. Four zwitterionic polymers with varying molecular structures-ranging from linear to five and six membered ring systems-were synthesized: poly(sulfobetaine methacrylamide) (pSBMAm), poly(sulfobetaine-1-vinylimidazole) (pSB1VI), poly(sulfobetaine-2-vinylpyridine) (pSB2VP), and poly(sulfobetaine-4-vinylpyridine) (pSB4VP).

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Hydrogen-Borrowing-Based Methods for the Construction of Quaternary Stereocentres.

Angew Chem Int Ed Engl

January 2025

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.

Compounds containing quaternary stereocentres are a valuable motif in biologically active compounds. Herein we present our strategy to utilise the hydrogen borrowing manifold to access α-quaternary ketones via a tandem acceptorless dehydrogenation-cyclisation cascade. This new application of the methodology results in the formation of five- and six-membered carbocycles with a high degree of diastereoselectivity.

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Heterocyclic compounds are increasingly used in medicinal chemistry because they are the main components of many biological processes and materials. Benzimidazole remains the core center of the heterocyclic chemical group, with essential traits such as six-five-member connected rings and two nitrogen atoms at the 1,3 position in a six-membered benzene and five-membered imidazole- fused ring system. Molecules with benzimidazole derivatives serve important functions as therapeutic agents and have shown excellent results in clinical and biological research.

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