The highly enantioselective cyclization of 3-alkenylindole via C-H activation has been established using Pd(OCOCF) in conjunction with the chiral spiro bis(isoxazoline) ligand (SPRIX). The presence of an N-allyl substituent on the substrate has a strong impact on both reactivity and selectivity, leading to tricyclic indole products (up to 96% ee) with a chiral quaternary carbon center.
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http://dx.doi.org/10.1039/c7cc03199h | DOI Listing |
Org Lett
January 2025
Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds & Materials, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, and College of Chemistry and Molecular Sciences, Wuhan University, 299 Bayi Rd, Wuhan 430072, China.
An enantioselective oxypalladation/malononitrile addition cascade reaction of alkyne-tethered malononitriles was reported to synthesize enaminones bearing an all-carbon quaternary center. Using Pd(TFA)/Pyox as a precatalyst, an array of enaminone products were obtained in moderate overall yields, with excellent er (93.5:6.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, United States.
The development of catalytic methods for the synthesis of enantiopure saturated heterocycles has been a long-standing challenge in asymmetric catalysis. We describe the first highly enantioselective palladium-catalyzed βC(sp)-H arylation and olefination of lactams for the preparation of various chiral N-heterocycles bearing quaternary carbon centers. The presence of strongly electron-withdrawing groups on the chiral bifunctional MPAThio ligand is crucial to the reactivity of weakly coordinating lactams.
View Article and Find Full Text PDFAnal Chem
January 2025
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
This study tackles the challenge of enantiodifferentiation of nitrile compounds, which is typically difficult to resolve using nuclear magnetic resonance (NMR) due to the significant distance between the chiral center and the nitrogen atom involved in molecular interactions. We have developed novel chiral F-labeled probes, each featuring two chiral centers, to exploit the "match-mismatch" effect, thereby enhancing enantiodiscrimination. This strategy effectively differentiates chiral analytes with quaternary chiral carbon centers as well as those with similar substituents at the chiral center.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Zhejiang Uiversity, Chemistry, 866 Yuhangtang Road, 310058, Hangzhou, CHINA.
Heck silylation of unactivated alkenes is an efficient strategy for the synthesis of useful organosilicon compounds. However, extensive efforts have been dedicated to only achieving achiral molecules. Herein, a highly regio- and enantioselective cobalt-catalyzed Heck silylation of unactivated alkenes with hydrosilanes is reported for the first time, providing access to axially chiral alkenes in good to excellent yields with 87-98% ee.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu Province, 225000, P. R. China.
Chalcogenides are the most important infrared nonlinear optical (NLO) material candidates, and the exploration of high-performance ones is attractive and challengeable. Hitherto, there is no NLO scandium (Sc) chalcogenides experimentally studied. Here, new quaternary Sc thiophosphate CsScPS (CSPS) was synthesized by the facile metal oxide-boron-sulfur/reactive flux hybrid solid-state method.
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