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http://dx.doi.org/10.1021/acs.orglett.2c01526 | DOI Listing |
Nat Commun
August 2025
Key Laboratory of Marine Drugs, Ministry of Education, Molecular Synthesis Center, and School of Medicine and Pharmacy, Ocean University of China, Qingdao, 266003, P. R. China.
J Org Chem
June 2025
School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China.
2-Aminoallyl cations serve as highly versatile intermediates in organic synthesis. Their cycloaddition with unsaturated compounds provides an efficient strategy for the construction of heterocycles, which are key structural motifs found in a wide range of natural products, bioactive molecules, and agrochemicals. The mechanism and enantioselectivity of the C,N-dipolar (3 + 2) cycloaddition of 2-aminoallyl cations with indoles have been investigated using density functional theory (DFT).
View Article and Find Full Text PDF[This corrects the article DOI: 10.1039/D2SC03966D.].
View Article and Find Full Text PDFUnlabelled: Due to the favorable chemical properties of mirrored chiral centers (such as improved stability, bioavailability, and membrane permeability) the computational design of D-peptides targeting biological L-proteins is a valuable area of research. To design these structures , a computational workflow should correctly dock and fold a peptide while maintaining chiral centers. The latest AlphaFold 3 (AF3) from Abramson et al.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2025
EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
Pyrazole heterocycles are prevalent in a wide range of medicinal and agrochemical compounds, and as such, the development of methods for their enantioselective incorporation into molecular scaffolds is highly desirable. This manuscript describes the effective formation of fused pyrazolo-pyridones and -pyranones in high enantioselectivity (up to >99:1 er) via an isoselenourea (HyperSe) catalyzed enantioselective [3 + 3]-Michael addition-cyclization process using readily available pyrazolylsulfonamides or pyrazolones as pronucleophiles and α,β-unsaturated anhydrides as starting materials. Mechanistic analysis indicates an unusual self-correcting reaction pathway involving preferential [1,2]-addition of the pronucleophile to initially generate an intermediate amide or ester that can be intercepted by isoselenourea acylation, leading to productive formation of the fused heterocyclic products with high enantiocontrol.
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