A series of new Mg(ii) amides featuring a bulky β-diketiminate backstop ligand, has been synthesised. These complexes are demonstrated to be excellent sources of nucleophilic amides that can participate in rapid C-F activation of several fluoroarenes at room temperature or using microwave assistance, leading to the installment of synthetically important C-N bonds via nucleophilic substitution.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/c9cc01670h | DOI Listing |
Dalton Trans
January 2025
Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
In this work, we show two synthetic routes to substitute the N position of mesoionic imines (MIIs). By Buchwald-Hartwig amination, 5-amino-1,2,3-triazoles can be arylated at the said position, showing the versatility of amino-triazoles as building blocks for MIIs. The reaction of MIIs with electrophiles (MeI, fluoro-arenes) highlights the nucleophilic nature of MIIs as even at room temperature aromatic C-F bonds can be activated with MIIs.
View Article and Find Full Text PDFNat Commun
November 2024
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, 610064, Chengdu, People's Republic of China.
Heavier group 14 carbene analogues, exhibiting transition-metal-like behavior, display remarkable capability for small molecule activation and coordination chemistry. However, their application in redox catalysis remains elusive. In this paper, we report the synthesis and isolation of a stannylene with carbodiphosphorane ligand.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Department of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, Aoba, Sendai 980-8578, Japan.
We herein propose that the catalytic concerted SAr reaction is a powerful method to prepare functionalized aromatic scaffolds. Classic stepwise SAr reactions involving addition/elimination processes require the use of electron-deficient aromatic halides to stabilize Meisenheimer intermediates, despite their widespread use in medicinal chemistry research. Recent efforts have been made to develop concerted SAr reactions involving a single transition state, allowing the use of electron-rich substrates based on the use of stoichiometric amounts of strong bases or reactive nucleophiles.
View Article and Find Full Text PDFChemosphere
August 2024
Department of Civil and Environmental Engineering and Institute of Construction and Environmental Engineering, Seoul National University, 1 Gwanak-ro Gwanak-gu, Seoul 08826, Republic of Korea. Electronic address:
Continuous growth in fluoroarene production has led to environmental pollution and health concerns owing to their persistence, which is attributed to the stable C-F bond in their structures. Herein, we investigated fluoroarene decomposition via hydrodefluorination using a rhodium-based catalyst, focusing on the effects of the chemical structure and functional group on the defluorination yield. Most compounds, except (pentafluoroethyl)benzene, exhibited full or partial reduction with pseudo-first-order rate constants in the range of 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2024
Department für Chemie und Biochemie, Universität Bern, Freiestrasse 3, 3012, Bern, Switzerland.
Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6-tetramethylpiperidide), s-block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!