We report a palladium-catalyzed method for 4,3- or 4,1-selective alkenylamination of terminal dienes. Three-component couplings proceed with alkenyl triflates and several amines, giving vicinal carboamination with a Xantphos-supported catalyst and distal difunctionalization with a phosphoramidite ligand. A number of constitutionally different disubstituted dienes also participate in regiodivergent carboaminations. Experimental evidence indicates that selectivity in the Xantphos reactions is largely influenced by the substrate, whereas the phosphoramidite-promoted process is catalyst controlled, orchestrated by a key π-stacking interaction among the ligand, solvent, and substrate.
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http://dx.doi.org/10.1021/jacs.3c09873 | DOI Listing |
J Org Chem
January 2025
Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China.
Among the known aromatic -heterocycles, pyrroles are significant and versatile privileged components in pharmacologically relevant molecules. Herein, we demonstrate a protocol for the selective construction of alkynylated pyrroles in a diversity-oriented fashion through divergent C2/C5 site-selective alkynylation of pyrrole derivatives by employing a palladium catalyst with two different solvent systems. In the presence of 1,4-dioxane, the C2-alkynylation process via chelation-assisted palladation is favored.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry and Biochemistry, Loyola University Chicago, Chicago, Illinois 60660, United States.
Chem Sci
December 2024
Leibniz-Institut für Katalyse e.V. Albert-Einstein-Straße 29a 18059 Rostock Germany
Nat Commun
June 2024
Department of Chemistry, University of Rochester, Rochester, NY, USA.
Olefin carbofunctionalization reactions are indispensable tools for constructing diverse, functionalized scaffolds from simple starting materials. However, achieving precise control over regioselectivity in intermolecular reactions remains a formidable challenge. Here, we demonstrate that using PAdBu as a ligand enables regioselective heteroannulation of o-bromoanilines with branched 1,3-dienes through ligand control.
View Article and Find Full Text PDFOrg Lett
May 2024
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
Controlling the regioselectivity for the alkoxycarbonylation of unsymmetric internal alkynes is challenging. Herein, a palladium-catalyzed ligand-controlled regiodivergent alkoxycarbonylation of internal trifluoromethylthiolated alkynes was achieved. A series of α- or β-SCF acrylates from the same trifluoromethylthiolated alkyne were obtained with moderate to high yield and regioselectivity.
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