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High-valent cyclopentadienyl cobalt catalysis is a versatile tool for sustainable C-H bond functionalizations. To harness the full potential of this strategy, control of the stereoselectivity of these processes is necessary. Herein, we report highly enantioselective intermolecular carboaminations of alkenes through C-H activation of N-phenoxyamides catalyzed by Co -complexes equipped with chiral cyclopentadienyl (Cp ) ligands. The method converts widely available acrylates as well as bicyclic olefins into attractive enantioenriched isotyrosine derivatives as well as elaborated amino-substituted bicyclic scaffolds under very mild conditions. The outlined reactivity is unique to the Cp Co complexes and is complementary to the reactivity of 4d- and 5d- precious-metal catalysts.
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http://dx.doi.org/10.1002/anie.202011140 | DOI Listing |
Angew Chem Int Ed Engl
August 2025
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
Under Ir-catalyzed conditions, N-2°-alkyl or N-3°-alkyl substituents of diverse tertiary aryl amides can be exchanged with the ortho-aryl C─H bond of the aromatic unit. These alkyl transfer processes employ a homochiral diphosphonite ligand, and this enforces notable levels of enantioconvergency for non-stereodefined 2°-alkyl substituents. Related processes allow the intermolecular transfer of N-2°-alkyl substituents, providing a convenient means of introducing difficult-to-install ortho-alkyl units.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, 15782, Spain.
An iridium complex featuring the perfluorinated bisphosphine ligand dppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using N-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes.
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.
View Article and Find Full Text PDFJACS Au
July 2025
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Organic nitriles are significant in pharmaceuticals, agrochemicals, cosmetics, and materials. Although numerous cyanidation methods have been developed, more eco-friendly and green protocols for manufacturing alkyl nitriles are in high demand. Here, we report a photoenzymatic enantioselective intermolecular hydrocyanoalkylation of alkenes catalyzed by flavin-dependent "ene"-reductases.
View Article and Find Full Text PDFOrg Lett
August 2025
School of Pharmaceutical Sciences (Shenzhen), Shenzhen Campus of Sun Yat-sen University, Shenzhen, 518107, P. R. China.
The first iridium-catalyzed direct intermolecular indole C7-allylic alkylation of 4-aminoindoles and racemic branched allylic esters was reported. Various substituted substrates were applicable to give the corresponding C7-allylated products in moderate to high yields (43-80%) with high regio- and enantioselectivities (82-99% ee) under mild reaction conditions. Representative transformations of the vinyl group in the product were carried out to examine the utility of this protocol.
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