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A palladium-catalyzed ring-opening oxo-formal [3 + 2]-cycloaddition reaction of novel donor-acceptor spirovinylcyclopropyl oxindole with 3-oxindole is described. The developed protocol provides facile access to oxo-bispirooxindole derivatives in good yields (up to 82% yield) with excellent diastereoselectivities (up to 20:1 dr).
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http://dx.doi.org/10.1021/acs.joc.8b02889 | DOI Listing |
Org Lett
July 2025
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.
We report a catalytic enantioselective total synthesis of an endocyclic alkene regioisomer of (-)-peduncularine, termed (-)-pseudo-peduncularine, and also a synthesis of its C7 epimer. Highlights of the syntheses include a new strategy for the construction of the peduncularine framework by palladium-catalyzed ynamide cycloisomerization/enamide reduction, which could be performed on a multigram scale. By introducing the indole side chain as a substituent on the ynamide, this approach contrasts with previous strategies that have relied on late-stage Fischer indole synthesis.
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May 2025
Advanced Research Institute and School of Pharmaceutical Sciences, Taizhou University, Jiaojiang, Zhejiang 318000, P. R. China.
A palladium-catalyzed three-component coupling of 2-arylaziridines, α-diazo esters, and cyclic ethers, affording tertiary enamides with excellent regio- and stereoselectivity, is reported. This regioselective ring-opening of aziridines is different from the classical transition-metal/phosphine catalyzed ones. A broad spectrum of substrates is tolerated (up to 33 examples).
View Article and Find Full Text PDFJ Org Chem
May 2025
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry & Pharmacy, Northwest A&F University, Yangling, Shaanxi 712100, China.
The first total synthesis of ansatrienol K, a novel trienomycin congener featuring a diene moiety within its 19-membered macrolactam ring, is reported. Key steps include two sequential palladium-catalyzed cross-coupling reactions for constructing the trisubstituted benzene ring and two distinct strategies for assembling the C6-C18 fragment. A Co(CO)-catalyzed carbonylative epoxide ring-opening provided the diene fragment, while late-stage Stewart-Grubbs catalyst-mediated diene-ene ring-closing metathesis (RCM) enabled efficient macrocyclization.
View Article and Find Full Text PDFJ Org Chem
May 2025
College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou 450001, China.
We report an efficient palladium-catalyzed ring-opening defluorinative Hiyama cross-coupling of -difluorocyclopropanes with structurally diverse (hetero)arylsilanes through C-C bond activation and C-F bond cleavage. This regioselective ring-opening defluorinative Hiyama cross-coupling features a broad substrate scope with excellent functional group compatibility, affording a diverse variety of linear 2-fluoroallylic scaffolds in good yields with high -selectivity.
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April 2025
Key Laboratory of Synthetic and Nature Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi'an 710127, China.
Palladium-catalyzed asymmetric transformations involving cyanide anions remain a challenge due to the strong affinity between cyanide anions and palladium, which induces alterations in the coordination sphere of the palladium center. Herein, palladium-catalyzed enantioselective cyanation is achieved via a ring-opening/cross-coupling process between aryl halide-tethered cyclobutanones and Zn(CN). This reaction is demonstrated to exhibit broad substrate scope and robust enantioselectivity.
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