10.1055/s-0037-1612422
The research aims to develop a new approach for the construction of quaternary stereogenic centers bearing nitrogen substituents in an enantioselective manner. The strategy leverages the [1,3]-chirality transfer from a chiral primary alcohol equivalent through an allyl cyanate-to-isocyanate rearrangement. The efficiency of this approach was demonstrated in the eight-step synthesis of the marine natural product (+)-geranyllinaloisocyanide, achieving an overall yield of 43%. Key chemicals used in the process include chiral primary alcohol equivalent, allyl cyanate, isocyanate, and various reagents such as diethylzinc, trichloroacetyl isocyanate, potassium carbonate, trifluoroacetic anhydride, N,N-diisopropylethylamine, lithium triethylborohydride, and cesium fluoride, among others. The study concluded that the allyl cyanate-to-isocyanate rearrangement with enantiomerically enriched α-silyl allyl alcohol is a highly effective method for chirality transfer, showcasing its potential for further applications in the synthesis of nitrogen-containing natural products.
10.1016/S0040-4039(00)99261-X
The research focuses on the synthesis of tetracyclic derivatives through 1,3-dipolar cycloaddition reactions involving β-carboline azomethine ylides. The purpose of the study was to develop a method for accessing a novel class of 11H-indolizino[8,7-b]indoles, which are potentially useful in the synthesis of biologically targeted β-carboline derivatives. The key conclusions were that the reactions allowed for the formation of these complex structures, with the major product being the 1:1 adduct, and that the formation of by-products could be minimized but not entirely prevented. The chemicals used in the process included trimethylsilylmethyl triflate, diethyl azodicarboxylate (DEAD), cesium fluoride, sodium ethanolate, and various β-carboline derivatives. The study also investigated the effect of temperature and concentration on product distribution, providing insights into optimizing the reaction conditions for the desired outcomes.
10.1007/BF00953645
The study investigates the intramolecular cyclization of pentafluorobenzene derivatives, focusing on the reaction of trimethylsilylpentafluorobenzene (I) with perfluoro-4-methyl-2-pentene (II) in the presence of cesium fluoride (CsF). This reaction unexpectedly yields approximately equal amounts of perfluoro-1,1,3-trimethylindane (IV) and perfluoro-4-methyl-2-phenyl-2-pentene (III). The authors propose a mechanism where the initial step involves nucleophilic pentafluorophenylation of olefin (II) by a complex of arylsilane (I) and CsF, leading to a perfluorinated carbanion (V). This carbanion can either lose a fluoride ion to form perfluorinated arylolefin (III) or undergo further reactions to form fluorinated indane (IV). The study also includes experimental details on the synthesis and characterization of these compounds, highlighting the unique formation of perfluoroindane derivatives through intramolecular nucleophilic cyclization.
10.2478/s11532-011-0104-9
The research focuses on the synthesis and characterization of a novel redox-active calix[4]arene-tetrathiafulvalene (TTF) dyad, which integrates the host properties of calix[4]arene with the redox characteristics of TTF. The experiments involved the preparation of the dyad through a series of chemical reactions, utilizing reactants such as p-tert-butylcalix[4]arene, tosylated TTF, and cesium fluoride. The structure of the synthesized dyad was confirmed using X-ray diffraction analysis, and its electrochemical properties were investigated by cyclic voltammetry, revealing two reversible one-electron redox waves. Additionally, UV-vis absorption spectra studies were conducted to assess the dyad's recognition properties for metal ions, particularly its interaction with Cu2+ and Hg2+, which led to the progressive oxidation of the TTF unit. Various analytical techniques were employed, including NMR, IR, and mass spectrometry, to characterize the synthesized compounds and intermediates.
10.1021/ol202395s
The research focuses on the insertion of benzynes into the PdN bond of P-alkenyl(alkynyl)-λ5-phosphazenes, leading to the formation of 1,4-benzazaphosphorinium triflates through a series of reactions including retro [2+2] cycloaddition/6π electrocyclization/protonation. The experiments involved the reaction of benzynes, generated from 2-(trimethylsilyl)phenyl triflates, with various P-alkenyl-λ5-phosphazenes in the presence of CsF as a reagent, using acetonitrile as a solvent. The reactions were carried out under a nitrogen atmosphere at 25°C, and the products were analyzed using analytical and spectral data, with some structures confirmed through X-ray crystal structure determination. The study also explored the scope of the reaction with different N-arylP-vinyl-λ5-phosphazenes, as well as related P-alkynyl derivatives and phosphane sulfides, optimizing conditions to achieve high yields of the desired products.
10.1021/ol800051k
The research focuses on the development of a mild and general method for the synthesis of benzofuran derivatives, which are prevalent in many biologically active compounds. The researchers utilized a cycloaddition reaction between arynes and iodonium ylides in the presence of cesium fluoride (CsF) as a catalyst, which allowed for the reaction of ortho-silyl aryltriflates with iodonium ylides at room temperature, yielding benzofurans in moderate to good yields. The study involved screening optimal reaction conditions using various bases and solvents, with CsF in acetonitrile proving to be the most effective. The experiments were conducted under an argon atmosphere, and the reactions were monitored using thin-layer chromatography (TLC) and gas chromatography (GC) analysis. The products were purified through extraction with diethyl ether, drying over anhydrous Na2SO4, and flash column chromatography. The structures of the synthesized benzofurans were confirmed using 1H and 13C NMR spectroscopy. The research also proposed a working mechanism for the reaction and discussed the regioselectivity observed in the products, attributing it to the properties of the reactants such as steric and electronic effects.
10.1134/S0036023612040080
The research investigates the phase formation in the system ZrO(NO?)?–H?PO?–CsF–H?O along the section at the molar ratio F/Zr = 1.5 and CsF/Zr = 2–5, with a ZrO? concentration of 2–5 wt% in the initial solution. The purpose is to explore the formation of new fluorophosphate zirconates and their properties. Key chemicals used include ZrO(NO?)?·2H?O, 85% H?PO?, and chemically pure CsF. The study identified new compounds such as CsH?Zr?F?(PO?)?·1.5H?O and two modifications of CsZrF?PO?·0.5H?O, along with the known phosphate zirconate CsZr?(PO?)?, obtained through calcination. The compounds were characterized using X-ray powder diffraction, IR spectroscopy, and thermal analysis. The conclusions highlight the formation of these new compounds and their thermal stability, with potential applications in areas such as X-ray luminescence.
10.1021/acs.orglett.1c01720
The study presents an efficient method for the trifluoromethylation of benzoic acids using TMSCF3 (trimethylsilyl trifluoromethane) to produce aryl trifluoromethyl ketones. The reaction involves anhydrides as in situ activating reagents, with trifluoroacetic anhydride (TFAA) and 4-dimethylaminopyridine (DMAP) playing crucial roles in activating the carboxylic acids and facilitating nucleophilic addition. CsF (cesium fluoride) is used to enhance the yield of the desired products. The reaction is conducted in PhOMe (anisole) solvent under nitrogen at 120 °C for 15 hours. The study demonstrates a wide substrate scope, including various carboxylic acids with different functional groups, and shows high functional group tolerance. Notably, bioactive molecules such as adapalin, probenecid, and telmisartan can also be trifluoromethylated using this method, highlighting its potential in drug design and development. The reaction conditions are relatively mild, and the process is scalable, making it a practical and environmentally benign approach for synthesizing aryl trifluoromethyl ketones.