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Migratory functionalization of C-H bonds through metal migration from carbon to carbon under transition metal catalysis is a process of significant academic and industrial interest. Herein, a palladium-catalyzed migratory cyclization of α-bromoalkene derivatives ArXCBr=CH, in which X denotes a phosphorus (P(O)R), silicon (SiR), sulfur (SO), carbon (C(O)), nitrogen (NTs), or oxygen-based moiety, affording various benzoheterocyclic compounds has been developed. Mechanistic investigations have demonstrated that the cyclization reaction proceeds through an unexpected cascade, with trans-1,2-palladium migration between sp carbons being a key step of catalytic cycle. To the best of our knowledge, this type of metal migration has not been reported previously.
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http://dx.doi.org/10.1038/s41467-025-58633-5 | DOI Listing |
Org Lett
August 2025
Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials (State Key Laboratory Cultivation Base), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, P. R. China.
The cyclopentachromene skeleton is a key structural motif in pharmaceutical and fluorescent materials. We here introduce a Pd-promoted double ring-closure strategy for tackling the modular synthesis of densely functionalized dihydrocyclopenta[]chromenes, which proceeds simply from two reaction partners with high diversity. This scheme features a reaction sequence beginning with 1,6-conjugate addition of -alkynyl quinone methide, followed by annulation and migratory insertion.
View Article and Find Full Text PDFChemphyschem
July 2025
Department of Basic Education, Shanxi Agricultural University, Taigu, Shanxi, 030801, P. R. China.
Hydrocarboxylation of olefins with HCOOH provides a practical method for the construction of various biologically and chemically relevant carboxylic acids. Density functional theory calculations have been performed on the detailed mechanisms of this reaction catalyzed by palladium complexes with TFPP and DPPB ligands, suggesting that the reaction preferably proceeds through sequential steps of the activation of anhydride, hydropalladation, CO migratory insertion, and the generation of a new anhydride followed by its decomposition and reductive elimination. For the Pd-TFPP system, the bis-coordinated pathway is favored over the monocoordinated pathway both kinetically and thermodynamically, governing anti-Markovnikov-selectivity.
View Article and Find Full Text PDFOrg Lett
June 2025
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, P. R. China.
A palladium-catalyzed carbo-cyanation reaction for synthesizing bulky nitriles with an all-carbon quaternary center via a "cut-and-sew" process of isocyanides is presented. The reaction proceeds through oxidative addition of indole-derived carbonate to Pd(0), followed by decarboxylation, migratory insertion, and the formation of a ketenimine intermediate. A geminate radical pair is formed, leading to radical coupling and the final bulky nitrile product.
View Article and Find Full Text PDFSci Adv
May 2025
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, E
Indoles represent one of the most robust and synthetically versatile classes of heteroaromatic compounds. However, the stereoselective conversion of planar indole rings into three-dimensional indoline skeletons bearing multiple stereogenic centers remains a persistent challenge in organic synthesis. Herein, we describe an intermolecular catalytic asymmetric dearomatization of simple indoles via a palladium-catalyzed three-component cross-coupling reaction.
View Article and Find Full Text PDFRSC Adv
May 2025
Department of Chemistry, College of Natural and Computational Sciences, Addis Ababa University P.O. Box 1176 Addis Ababa Ethiopia.
Palladium-catalyzed Suzuki-Miyaura Coupling (SMC) is a powerful strategy to construct C-C bonds; however, it suffers from the disadvantages of using expensive palladium catalysts and additives. Based on the experimental development of the base-free nickel catalyzed Suzuki-Miyaura coupling of acid fluorides (ArC(O)F) with diboron reagent, we carried out DFT calculations to gain insight into the reaction mechanisms. The coupling reaction proceeds four stages: (1) oxidative addition of the acid fluoride to the Ni(0) center to break the C-F bond, (2) transmetalation with diboron reagent, (3) carbonyl deinsertion reverse carbonyl migratory insertion, and (4) reductive elimination to afford the coupling product and regenerate the active catalyst.
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