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An enantioselective Pd-catalyzed intramolecular dearomative reductive Heck reaction of -(-bromoaryl) indole-3-carboxamide is developed. By employing Pd(dba)/SPINOL-based phosphoramidite as the chiral catalyst and HCONa as the hydride source, a series of enantioenriched spiro indolines bearing vicinal stereocenters were afforded in moderate to good yields with excellent enantioselectivities. The reductive Heck reaction of formal tetrasubstituted alkene bearing β-hydrogens is therefore realized by inhibiting β-H elimination.
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http://dx.doi.org/10.1021/acs.orglett.4c00775 | DOI Listing |
ACS Catal
May 2025
University of Texas at Austin, Department of Chemistry Welch Hall (A5300), 105 E 24th St., Austin, TX 78712, USA.
Catalytic methods for the intermolecular formate-mediated C-C coupling of Csp-X pronucleophiles beyond reductive Heck reactions (alkene hydroarylations) are catalogued. These methods include transfer hydrogenative reductive couplings of aryl/vinyl halides or triflates to carbonyl compounds (Grignard/NHK-type reactions), as well as reductive cross-couplings of two aryl/vinyl halide or triflate partners. These studies demonstrate that reactions traditionally associated with discrete Csp carbanions can be rendered catalytic and free from premetalated reagents or metallic reductants using sodium or potassium formate - abundant, low molecular weight sources of hydrogen.
View Article and Find Full Text PDFBioorg Chem
August 2025
School of Pharmacy, Yantai University, Yantai 264005, PR China. Electronic address:
Sepsis-induced acute lung injury (ALI) is a critical health concern with high morbidity and mortality, while its effective treatment options are limited. Our previous study, identified forsyqinlingine C (FC), a novel C9-monoterpenoid alkaloid from the ripe fruit of Forsythia suspensa (Thunb.) Vahl, exhibits notable anti-inflammatory activity.
View Article and Find Full Text PDFChem Sci
August 2025
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU) Xi'an 710062 P. R. China
Axially chiral olefins represent an underexplored class of atropoisomers given their conformational flexibility and relatively low configurational stability. Atroposelective access to axially chiral olefins formation of a chiral axis is challenging. Reported herein is palladium-catalyzed redox-diversified olefination of aryl halides with two classes of bifunctional alkynes based on rational design of catalytic systems.
View Article and Find Full Text PDFChem Commun (Camb)
July 2025
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016, India.
Herein, we present an enantioselective, fluorine-retentive Pd-catalyzed reductive Heck cyclization reaction of fluorinated alkenes, enabling the synthesis of all-carbon quaternary 3,3-disubstituted fluoroalkyl-tethered oxindoles. Control experiments and DFT studies have provided insights into the reaction mechanism and stereochemical induction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
Overriding the inherent substrate-controlled regioselectivity in aziridine activation holds significant potential. It could enable previously inaccessible disconnections from these readily available, strained heterocycles, facilitating the diverse synthesis of nitrogen-containing products. In this study, we present a Ni-catalyzed dynamic kinetic activation of 2-alkyl (and 2,2-dialkyl) aziridines, leading to unconventional branched-selective alkyl Heck-type coupling with styrenes and reductive defluorinative coupling with trifluoromethyl alkenes.
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