We report the construction of unsymmetrical dimeric carbazoles and π-extended bis carbazoles (having an aryl ring spacer) via the C-H functionalization route. Generally, oxidative coupling and traditional cross-coupling reactions have been used to construct bis- and π-extended carbazoles. Natural bis carbazole alkaloids and synthetic dimeric carbazoles are important molecules in medicinal, materials chemistry research. There is scope for developing new synthetic transformations leading to structurally appealing bis carbazoles. The synthesis of symmetrical bis carbazoles via cross-coupling and C-H functionalization is well known in the literature and it is noted that there exist limited reports on the construction of unsymmetrical bis carbazoles via the C-H functionalization route. Accordingly, this paper reveals the Pd(II)-catalyzed bidentate directing group-assisted C-H functionalization as a progressive route for the synthesis of a library of unsymmetrical dimeric carbazoles and π-extended bis carbazoles (connected through an aryl ring spacer).
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http://dx.doi.org/10.1002/asia.202401353 | DOI Listing |
Acta Crystallogr E Crystallogr Commun
January 2025
Osaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan.
The asymmetric unit of the title compound is composed of one host mol-ecule, -4-(1 ,5 -3-aza-1,5(3,9)-dicarbazola-cyclo-octa-phane-3-yl)benzo-nitrile and one di-chloro-methane solvate mol-ecule, CHN·CHCl. The host mol-ecule possesses a planar chirality but crystallizes as a racemate in the space group 2/. It adopts an -configuration, in which two carbazole rings are partially overlapped with a parallel orientation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Okayama Daigaku Daigakuin Shizen Kagaku Kenkyuka, Division of Applied Chemistry, JAPAN.
Intramolecular aromatic oxidative coupling of 3,6-bis(m-terphenyl-2'-yl)carbazole provided a bis(m-terphenyl)-fused carbazole, while that of 3,6-bis(m-terphenyl-2'-yl)-1,8-diphenylcarbazole afforded a bis(quaterphenyl)-fused carbazole. Borylation of the latter furnished a B,N-embedded helical nanographene binding a fluoride anion via a structural change from the three-coordinate boron to the four-coordinate boron. The anionic charge derived from the fluoride anion is stabilized over the expanded p-framework, which leads to the high binding constant (Ka) of 1 × 105 M-1.
View Article and Find Full Text PDFChem Asian J
January 2025
Mahidol University Faculty of Science, Chemistry, Rama VI Road, 10400, Bangkok, THAILAND.
Described herein is a facile electrochemical strategy for the generation of formaldehyde from N,N-dimethylacetamide (DMA) and water (H2O) toward a direct and site-selective N-hydroxymethylation of indoles and derivatives. Mechanistic studies suggested that N-(hydroxymethyl)-N-methylacetamide generated in situ from DMA/H2O under electrochemical conditions serves as a formaldehyde surrogate. The developed methodology features mild, base- and metal catalyst-free conditions.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Département de chimie, Université de Sherbrooke, Sherbrooke, Québec J1K 2R1, Canada.
ACS Omega
December 2024
Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos, São Paulo CEP 12228-900, Brazil.
The five-coordinate complex [RuCl(PNP)] () was synthesized from the binuclear [RuCl(-cym)] with a PNP-type ligand (PNP = 3,6-di--butyl-1,8-bis(dipropylphosphino)methyl)-9-carbazole - (Cbzdiphos )H) in a toluene solution, within 20 h at 110 °C, producing a green solid, which was precipitated with a 1/1 mixture of - pentane/HMDSO. The complex was characterized by NMR-H, C, and P{H}, mass spectroscopy-LIFDI, FTIR, UV/vis spectroscopy, and cyclic voltammetry, as well as a description of the optimized structure by DFT calculation. The reactivity of was investigated in the presence of potassium triethylborohydride (KBEtH, in THF solution of 1.
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