Sulfonimidamides and Imidosulfuric Diamides: Compounds from an Underexplored Part of Biologically Relevant Chemical Space

Two novel solid reagents—1-sulfonimidoyl- and 1-sulfamimidoyl-3-methylimidazolium derivatives—for the synthesis of sulfonimidamides and imidosulfuric diamides, respectively, were developed. It is shown that these reagents are very effective in substitution reactions with various N- and O-nucleophiles; therefore, they significantly extend the accessibility to the chemical space covered by organosulfur(VI) compounds with S=N bonds. In addition, previously unknown imidosulfuric diamides with free imino nitrogen groups were prepared, and their physical and chemical properties were characterized (including molecular geometry, pK_a, Log P, microsomal stability, and reactivity towards typical electrophiles). Similar to other organosulfur(VI) derivatives with S=N bonds, these compounds can be considered as promising bioisosteres of amides, ureas, or sulfonamides.     

Nickel(ii) N-heterocyclic carbene complexes as efficient catalysts for the Suzuki—Miyaura reaction

Russian Chemical Bulletin - Catalytic activity of nickel(ii) and palladium(ii) N-heterocyclic carbene (NHC) complexes derived from imidazole, benzimidazole, and 1,2,4-triazole was comparatively...     

Saturated Boronic Acids,Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron-containing drugs are surveyed, with special emphasis on α-amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp³)−C and C(sp³)-heteroatom bonds is given, including recent developments in the Suzuki-Miyaura and Chan-Lam cross-couplings, single-electron-transfer processes including metallo- and organocatalytic photoredox reactions, and transformations of boron “ate” complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the “classical” methods (transmetallation of organolithium/magnesium reagents with boron species, anti-Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative C−H activation, novel approaches to alkene hydroboration, and 1,2-metallate-type rearrangements).     

Synthesis of 5-Hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano[2,3-c]pyridin-2-ones and Their Esters

New 5-hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano-[2,3-c]pyridin-2-ones and their esters were synthesized. The structure of obtained compounds was determined through a complete ¹H NMR analysis.     

Estimation Problems for Periodically Correlated Isotropic Random Fields

Spectral theory of isotropic random fields in Euclidean space developed by M. I. Yadrenko is exploited to find a solution to the problem of optimal linear estimation of the functional

$$ A\zeta ={\sum\limits_{t=0}^{\infty}}\,\,\,{\int_{S_n}} \,\,a(t,x)\zeta (t,x)\,m_n(dx) $$

which depends on unknown values of a periodically correlated (cyclostationary with period T) with respect to time isotropic on the sphere S _n in Euclidean space E ⁿ random field ζ(t, x), t?∈?Z, x?∈?S _n . Estimates are based on observations of the field ζ(t, x)?+?θ(t, x) at points (t, x), t?=???1,???2, ..., x?∈?S _n , where θ(t, x) is an uncorrelated with ζ(t, x) periodically correlated with respect to time isotropic on the sphere S _n random field. Formulas for computing the value of the mean-square error and the spectral characteristic of the optimal linear estimate of the functional Aζ are obtained. The least favourable spectral densities and the minimax (robust) spectral characteristics of the optimal estimates of the functional Aζ are determined for some special classes of spectral densities.

     

The influence of Au-nanoparticles presence in PDMS on microstructures creation by ion beam lithography

3D microstructures in pure poly(dimethylsiloxane) (PDMS) and PDMS with embedded Au nanoparticles were prepared by ion beam lithography without any further etching. Two mega-electron volts helium and 10 MeV oxygen ions were used for ion microstructuring. Parallel lines of 1 mm in length and 10 μm in thickness were fabricated for investigation of the effect of the nanoparticles presence in the polymer on the surface morphology of the created microstructures. The created microstructures were checked by optical microscope. Infrared (IR) spectrometry was used to study the effect of the ions type and fluence on the chemical changes of the material. Atomic force microscopy was used for the fine detail study as well as for checking the microstructure quality. Analysis revealed an increased radiation resistance of the nanocomposite compared to the pure PDMS. Shrinkage is proportional to the fluence, but the maximum value for both materials is limited by saturation. 3D microstructure in modified PDMS obtained at the same irradiation condition as pure PDMS is characterized by its smaller height. Obtaining the microstructure in nanocomposite of the same height as in pure PDMS by increasing the fluence can be impossible due to saturation of shrinkage and/or radiation-induced heating of the material.     

Direct Spectroscopic Detection of the Orientation of Free OH Groups in Methyl Lactate–(Water)1,2 Clusters: Hydration of a Chiral Hydroxy Ester

Hydration of chiral molecules is a subject of significant current interest in light of recent experimental observations of chirality transfer from chiral solutes to water in solution and the important roles which water plays in biological events. Using a broadband chirped pulse and a cavity based microwave spectrometer, we detected spectroscopic signatures of the mono‐ and dihydrates of methyl lactate, a chiral hydroxy ester. Surprisingly, these small hydration clusters show highly specific binding preferences. Not only do they strongly prefer the insertion H‐bonding topology, but they also favor specific pointing direction(s) for their non‐H‐bonded hydroxy group(s). We observed that the particular dihydrate conformer identified is not the most stable one predicted. This work highlights the superior capability of high‐resolution spectroscopy to identify specific water binding topologies, and provides quantitative data to test state‐of‐the‐art theory.