In the title system, OCNXeOSO2CF3 is formed, which readily oxidises iodobenzene to PhI+–NCO –OTf. The direct amination of aromatic substrates is possible with the use of XeF2–Me3SiNCO–CF3SO3H.
The title reactions lead to the corresponding β-fluoroisocyanates and β-isocyanatotriflates with the formation of the intermediates FXeNCO and OCNXeOSO2CF3.
Trimethylsilyl cyanide reacts with isocyanates to give 12 cycloadducts, 5-(trimethylsilylimino)imidazolidine-2,4-diones, in high yield. The reaction of trimethylsilyl cyanide with carbodiimides proceeded in the presence of a catalytic amount of aluminum trichloride to afford 11 adducts, N-trimet...
Silyl group at the nitrogen atom in the O-silylurethanes drastically affects the thermolysis processes and allows one to simplify the synthesis of methyl- and trimethylsilyl isocyanates.
A variety of ketoximes undergo the Beckmann rearrangement when heated with 0.5 molar equiv. of chloral (neat melt/∼130°C), to furnish the corresponding amides in excellent yields (generally 80–95%) after simple work-up. (Aromatic aldoximes dehydrated to the corresponding nitriles in excellent...
Upon exposure to methoxymethylamine and BOP, the stable hydroxybenzotriazolyl amide of TrPheOH was isolated instead of the expected Weinreb amide. This amide behaves as an active amide similar to the Weinreb amide and could be used, among others, for the synthesis of t-Bu esters. Reaction of N-t...
The conformations of various conformers of the molecules methylaminomethanol, 1-methoxymethylamine and 1-methoxy-N,N-dimethylmethylamine, all of which contain an N-C-O unit, were determined by an ab initio method using the 4-21G basis set and complete geometrical optimization. The results were i...
Earlier work has demonstrated the irreversible inactivation of serine and cysteine proteinases by peptides with a C-terminal chloromethyl ketone group. With a C-terminal diazomethyl ketone, on the other hand, peptides become reagents specific for cysteine proteinases. We have now synthesized and...
The formation of azines in the reaction of diazoethane with α-diazo-p-nitroacetophenone and α-diazo-p-nitropropiophenone has been confirmed by the elucidation of the nature of certain of their further reaction products.
Energy distributions over vinyl chloride photofragment in 3-chloro-3-methyldiazirine photolysis at 416, 365 and 337 nm in SF6, and over ethylene in 3-methyldiazirine photolysis at 313 nm and in diazoethane at 435 and 250 nm have been calculated by direct deconvolution of experimental results. A ...
A novel direct synthesis of 1,3-dioxo-substituted allenes was developed by copper(I)-catalyzed coupling of α-oxo-alkynes and α-oxo-diazos. It was a sequence of adding substrates-controlled method and the desired products were synthesized chemoselectively by adding α-oxo-alkyne terminally.
Two push-pull chromophores that have shown utility in the field of molecular electronics and non-linear optics are DDMEBT (1, 2-(4-dimethylamino)phenyl)-3-((4-(dimethylamino)phenyl)ethynyl)buta-1,3-diene-1,1,4,4-tetracarbonitrile) and TDMEE (2, 4-(4-dimethylamino)phenyl)but-1-en-3-yne-1,1,2-tric...
Because metal nanoparticles have a high surface area to volume ratio, they can be highly reactive, cost-effective catalysts. However, metallic surfaces are usually too reactive to maintain their metallic character in the presence of oxygen and/or water vapor. Metal nanoparticle catalysts must be...
An oxygen-sensitive gel material containing platinum-acetylide was successfully synthesized using covalent linkages between the isocyanate groups on the platinum-acetylide crosslinker and the hydroxyl groups on commodity polymers. It was shown that the elasticity of the gel could be tailored by ...
The structurally well-defined copper(I) acetate was immobilized on silica gel via electrostatic interactions. The catalytic activity of the immobilized catalyst Cu(I)–SiO2 was examined in the click synthesis of 1,2,3-triazoles in water/ethanol at room temperature. The catalyst showed high catal...
Trinuclear copper(I) and silver(I) acetylide complexes containing carboxylate group, [Cu3(μ-dppm)3(μ3-η1-C ≡ CCOO)(μ3-OCH3)] and [Ag3(μ-dppm)3(μ3-η1-C ≡ CCOO)(μ3-Cl)], have been synthesized and their photophysical properties investigated (dppm = bis(diphenylphosphino)methane). Their X-...
A series of trinuclear copper(I) acetylide complexes with carbonyl moiety, [Cu3(μ-dppm)3(μ3-η1-CCC(O)R)2](ClO4) (R = H (1), CH3 (2), OCH3 (3), NH2 (4), NEt2 (5)) (dppm = bis(diphenylphosphino)methane), have been synthesized and characterized. The crystal structures of [Cu3(μ-dppm)3(μ3-η1-C...
Copper acetylides are readily available and especially convenient reagents for the alkynylation of a broad range of heteronucleophiles. Upon simple activation with molecular oxygen in the presence of suitable ligands and solvents, they readily transfer their alkyne moiety at room temperature, no...
The most current applications of copper(I)-mediated reactions of alkynes involving copper(I)–acetylide are presented. This review focuses on the mechanistic understanding of these transformations and the effect of the metal acetylides in the reaction pathways.
Titanium silicalite (TS-1) loaded with sulfated zirconia as bifunctional oxidative and acidic catalyst has been synthesized at various loadings of zirconium (2–20 wt%). Structure and properties of the samples were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR),...
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