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The enantioselective conjugate addition of malonates to α,β-unsaturated aldehydes catalysed by 4-oxalocrotonate tautomerase is described. High conversions, high enantioselectivities, and good isolation yields were achieved for a range of substrates. We further completed a four-step synthesis of the antidepressant (+)-femoxetine by utilizing this reaction and an enzymatic reductive amination reaction.
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http://dx.doi.org/10.1039/d3ob00111c | DOI Listing |
Org Lett
September 2025
State Key Laboratory of Precision and Intelligent Chemistry, Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China.
A novel palladium-catalyzed asymmetric aminomethylative pyridonation of conjugated dienes with -acetals and 2-hydroxypyridines was established, which provided a direct and reliable method for the synthesis of a wide range of γ-aminated N-substituted 2-pyridones with good to excellent enantioselectivities. The simple BF was identified as an effective cocatalyst to improve the reaction efficiency, and DFT calculations revealed that proton transfer between the aminomethylated allylic palladium species and 2-hydroxypyridine promoted by BF is crucial for obtaining good reactivity.
View Article and Find Full Text PDFAppl Environ Microbiol
August 2025
Department of Plant and Microbial Biology, North Carolina State University, Raleigh, North Carolina, USA.
Isobutylene (IB) is produced on a large scale by the petrochemical industry and is metabolized by the aerobic alkene-metabolizing bacterium sp. ELW1. The initial metabolite of IB catabolism by this bacterium is proposed to be 2-methyl-1,2-epoxypropane (isobutylene oxide [IBO]).
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
We report herein an enantioselective total synthesis of (-)-psathyrin A, an antibacterial diterpene natural product possessing a unique 6/4/5/5 tetracyclic carbon skeleton and seven contiguous stereocenters, including three adjacent all-carbon quaternary centers. Our synthesis begins with commercially available 2-methyl-2-cyclopenten-1-one, which was subjected to an enantioselective copper/NHC-catalyzed conjugate addition, followed by trapping the resulting enolate with 1-bromo-2-butyne to set up the first two stereocenters, including one all-carbon quaternary center. A Suzuki-Miyaura cross coupling introduces an aromatic ring as the six-membered ring precursor, and a gold(I)-catalyzed Conia-ene reaction constructs the 5/5-fused bicyclic ring system and the second all-carbon quaternary center.
View Article and Find Full Text PDFOrg Lett
September 2025
Departament de Química Orgànica, Facultat de Química, Universitat de València, C. Dr. Moliner 50, 46100 Burjassot, Spain.
Vinylogous isocyano esters were prepared for the first time. They react with aldehydes to give chiral oxazolines bearing a pendant conjugated ester under synergistic silver/organocatalysis. The reaction is carried out using a bifunctional squaramide in combination with silver oxide and performs well with a number of aryl, heteroaryl, and cycloalkyl aldehydes, providing the expected heterocycles in good yields with good diastereoselectivity and enantiomeric excesses ranging from 60% to 95% ee.
View Article and Find Full Text PDFCell Chem Biol
August 2025
Department of Pharmaceutics, Wuya College of Innovation, Shenyang Pharmaceutical University, Shenyang 110016, China; Joint International Research Laboratory of Intelligent Drug Delivery Systems, Ministry of Education, Shenyang, China. Electronic address:
Designing highly selective nanomedicines with precise recognition of biological interfaces for efficient cancer therapy represents a tremendous challenge. Inspired by the inherent chirality and enantioselectivity of organisms, we constructed dynamic chiral cyclic diselenide-conjugated paclitaxel prodrug nanoassemblies (CSEPNs) to simulate the chiral recognition process. The optimal chiral configuration with potent antitumor effects was screened by deconstructing the lock-and-key biorecognition of CSEPNs.
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