A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O⋅⋅⋅K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C-H activation/borylation.
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http://dx.doi.org/10.1002/anie.201809929 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Tsinghua University, Department of Chemistry, 1 Qinghuayuan, Haidian District, 100084, Beijing, CHINA.
The in-depth research on the charge transport properties of BN-embedded polycyclic aromatic hydrocarbons (BN-PAHs) still lags far behind studies of their emitting properties. Herein, we report the successfully synthesis of novel ladder-type BN-PAHs (BCNL1 and BCNL2) featuring a highly ordered BC3N2 acene unit, achieved via a nitrogen-directed tandem C-H borylation. Single-crystal X-ray diffraction analysis unambiguously revealed their unique and compact herringbone packing structures.
View Article and Find Full Text PDFDalton Trans
December 2024
Institute of Chemistry, Faculty of Natural Sciences II, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Str. 2, D-06120 Halle (Saale), Germany.
The formation of a rhodium pincer-type complex with a boron-based donor ligand and its reactivity are reported. The starting complex contains a formal borylene moiety, stabilised by two pyridine substituents. Quantum chemical investigations indicate the possibility of deprotonation of the central donor group of the type pyBH in this complex.
View Article and Find Full Text PDFNat Commun
November 2024
College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy for the activation of aryl thianthrenium salts using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating the need for external donors. Utilizing this EnT approach, we achieve C-H deuteration of arenes under visible light with CDCl as a deuterium source to synthesize various deuterated aromatic compounds, including important natural products and pharmaceuticals.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Institut für Anorganische Chemie and Institute for Sustainable Chemistry & Catalysis with Boron, Universität Würzburg, Am Hubland, Würzburg 97074, Germany.
Herein, we report the first 1,4-Pd aryl to aryl migration/Miyaura borylation tandem reaction in fused systems. The Pd shift occurred in the bay region of the dibenzo[,]chrysene building blocks, giving rise to a thermodynamically controlled mixture of 1,8- and 1,9-borylated compounds that allowed the preparation of regioisomeric azaborole multihelicenes from the same starting material. The outcome of this synthesis can be controlled by the choice of reaction conditions, allowing the migration process to be turned off in the absence of an acetate additive and the target multiheterohelicenes to be prepared in a regioselective manner.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
State Key Laboratory of Elemento-Organic Chemistry and Frontiers Science Center of New Organic Matter, Nankai University, Tianjin 300071, People's Republic of China.
Controlled oxidation of NHB-stabilized disilyne (NHB)Si ≡ Si(NHB) (, NHB = [ArN(CMe)NAr]B, Ar = 2,6-PrCH) with one equivalent of trimethylamine N-oxide (MeN─O) in dry -hexane gave oxo-bridged bis-silepin in high yields. DFT calculations disclosed that silepin is only more stable by 13.4 kcal/mol than the corresponding oxo-bridged bis-silylene intermediate (NHB)Si(μ-O)Si(NHB), and was very likely to be formed by the insertion of the two divalent Si atoms into the pendant aryl rings in bis-silylene intermediate .
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