A series of air- and moisture-stable iminoisoindoline-based palladacycles have been prepared in two operationally simple steps from commercially available reagents. para-Substituted N,N'-diphenyliminoisoindoline ligands are easily synthesized from phthalaldehyde and para-substituted anilines and further reaction of the iminoisoindoline ligands with Pd(OAc)(2) in dichloromethane at room temperature results in formation of six-membered [C,N] dinuclear cyclopalladated complexes with the general formula [(iminoisoindoline)Pd(micro-OAc)](2). The resulting palladacyclic complexes were tested as precatalysts in Heck and Suzuki coupling reactions.
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http://dx.doi.org/10.1039/b806544f | DOI Listing |
Chem Sci
December 2024
Department of Chemistry, Indian Institute of Technology Madras Chennai 600036 India
An intermolecular carboamination reaction of allyl amines under Pd(ii)-catalysis is reported, expediting the synthesis of valuable vicinal diamines embedded in a functionally enriched linear carbon framework with high yields and exclusive Markovnikov selectivity. Central to our approach is the strategic use of a removable picolinamide auxiliary, which directs the regioselectivity during aminopalladation and stabilizes the crucial 5,5-palladacycle intermediate. This stabilization facilitates oxidative addition to carbon electrophiles, enabling the simultaneous incorporation of diverse aryl/styryl groups as well as important amine motifs, such as sulfoximines and anilines, across carbon-carbon double bonds.
View Article and Find Full Text PDFChem Sci
December 2024
School of Chemistry and Chemical Engineering, Hainan University Haikou 570228 China
Nat Commun
November 2024
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China.
Palladium-catalyzed directed C - H functionalization/cyclization is an effective approach for synthesizing nitrogen heterocycles. Imine, known for its ease of installation/removal, has been extensively used in the C-H activation of aldehydes, ketones, and alkylamines. Nevertheless, it has been rarely explored in the C(sp)-H activation of aryl amines because of the generation of a strained four-membered palladacycle.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Asymmetric de novo synthesis of benzocyclobutenes (BCBs) via catalytic intermolecular reaction is highly desired for efficient access to this important class of compounds, yet such a strategy remains unmet challenge. Here, we report a Pd/Pyrox-catalyzed asymmetric [2+2] annulation between arylboronic acids and functionalized alkenes, providing an unprecedented efficient protocol to access various enantio-enriched BCBs in a modular and versatile manner under mild conditions. A broad substrate scope with excellent enantioselectivity has been achieved under the current protocol.
View Article and Find Full Text PDFACS Cent Sci
October 2024
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong 999077, P.R. China.
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