Post-synthetic conversion of the trifluoromethyl group to a heteroaryl group at the C5 position of the pyrimidine base in DNA oligonucleotides was achieved. Specifically, the oligonucleotides containing 5-trifluoromethylpyrimidine bases were treated with -phenylenediamines and -aminothiophenols as nucleophiles to afford the corresponding 5-(benzimidazol-2-yl)- and 5-(benzothiazol-2-yl)-pyrimidine-modified bases. Furthermore, evaluation of the fluorescence properties of the obtained oligonucleotides revealed that among them the oligonucleotide containing 5-(5-methylbenzimidazol-2-yl)cytosine exhibited the highest fluorescence intensity. These results indicated that post-synthetic trifluoromethyl conversion, which is practical and operationally simple, is a powerful tool for exploring functional oligonucleotides.
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http://dx.doi.org/10.1039/d4ob00402g | DOI Listing |
Org Biomol Chem
May 2024
Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Nishihama, Yamashiro-cho, Tokushima 770-8514, Japan.
Post-synthetic conversion of the trifluoromethyl group to a heteroaryl group at the C5 position of the pyrimidine base in DNA oligonucleotides was achieved. Specifically, the oligonucleotides containing 5-trifluoromethylpyrimidine bases were treated with -phenylenediamines and -aminothiophenols as nucleophiles to afford the corresponding 5-(benzimidazol-2-yl)- and 5-(benzothiazol-2-yl)-pyrimidine-modified bases. Furthermore, evaluation of the fluorescence properties of the obtained oligonucleotides revealed that among them the oligonucleotide containing 5-(5-methylbenzimidazol-2-yl)cytosine exhibited the highest fluorescence intensity.
View Article and Find Full Text PDFOrg Biomol Chem
December 2023
Department of Chemistry, Laboratory of Catalysis and Organic Synthesis, Indian Institute of Technology Roorkee, Roorkee-247667, Uttarakhand, India.
This review highlights the recent advances, from 2015 to 2023, on the introduction of organo-fluorine derivatives at the N-heteroarene core. Notable features considering new technologies based on organofluorine compounds such as: (i) approaches based on non-precious metal catalysis (Fe, Co, Mn, Ni, .), (ii) the development of new strategies using non-precious metal-catalysts for the introduction of organo-fluorinine derivatives using N-heterocycles with one or more heteroatoms, (iii) newer reagents for fluorination, difluoromethylation, trifluoromethylation, or perfluoroalkylation of N-heteroarenes using different approaches, (iv) mechanistic studies on various catalytic transformations, as and when required, and (v) the synthetic applications of various bio-active organo-fluorine compounds, including post-synthetic drug derivatization, are discussed.
View Article and Find Full Text PDFChemistry
September 2021
Univ Rennes, CNRS, UMR6226, 3500, Rennes, France.
The utility of C-H bond functionalization of metalated ligands for the elaboration of aryl-functionalized difluorinated-1-arylisoquinolinyl Ir(III) complexes has been explored. Bis[(3,5-difluorophenyl)isoquinolinyl](2,2,6,6-tetramethyl-3,5-heptanedionato) iridium(III) undergoes Pd-catalyzed C-H bond arylation with aryl bromides. The reaction regioselectively occurred at the C-H bond flanked by the two fluorine atoms of the difluoroaryl unit, and on both cyclometalated ligands.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2021
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, 210023, P. R. China.
Post-synthetic modification (PSM) is a prevalent and powerful strategy to introduce desired functionalities into covalent organic frameworks (COFs) for functional products, expediting their applications vastly. Herein, we demonstrate a PSM strategy for functionalizing brominated COFs via the well-developed Suzuki-Miyaura cross-coupling. By this, a variety of functionalities were installed into COFs efficiently, while the crystallinity and porosity of COFs was well-retained.
View Article and Find Full Text PDFChemistry
July 2020
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Known for excellent stability, porosity and functionality, the high-valent Zr metal-organic frameworks (Zr-MOFs) still meets synthetic challenge in modulating the strength of Zr-O linkage. Herein we explore the unusual coordination dynamics of fluorinated Zr-MOFs by designing two trifluoromethyl modified ligands with distinct geometry preference to form a family of thermodynamic and kinetic products. The low-connecting kinetic Zr-MOFs possess substitutable coordination sites to endow Zr -cluster with extra dynamic behaviors, thus opening a post-synthetic pathway to sequential reassembly/disassembly processes.
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