Pd-Catalyzed Difluoromethylations of Aryl Boronic Acids,Halides, and Pseudohalides with ICF2H Generated ex Situ

An expedient ex-situ generation of difluoroiodomethane (DFIM) and its immediate use in a Pd-catalyzed difluoromethylation of aryl boronic acids and ester derivatives in a two-chamber reactor is reported. Heating a solution of bromodifluoroacetic acid with sodium iodide in sulfolane proved to be effective for the generation of near stoichiometric amounts of DFIM for the ensuing catalytic coupling step. A two-step difluoromethylation of aryl (pseudo)halides with tetrahydroxydiboron as a low-cost reducing agent, both promoted by Pd catalysis, proved effective to install this fluorine-containing C₁ group onto several pharmaceutically relevant molecules. Finally, the method proved adaptable to deuterium incorporation by simply adding D₂O to the DFIM-generating chamber.     

Chemoselective Acylation of Nucleosides

Acylated nucleoside analogues play an important role in medicinal chemistry and are extremely useful precursors to various other nucleoside analogues. However, chemoselective acylation of nucleosides usually requires several protection and deprotection steps due to the competing nucleophilicity of hydroxy and amino groups. In contrast, direct protecting-group-free chemoselective acylation of nucleosides is a preferred strategy due to lower cost and fewer overall synthetic steps. Herein, a simple and efficient chemoselective acylation of nucleosides and nucleotides under mild reaction conditions, giving either O- or N-acylated products respectively with excellent chemoselectivity is reported.     

Halide-Free Synthesis of New Difluoro(oxalato)borate [DFOB]−-Based Ionic Liquids and Organic Ionic Plastic Crystals

The implementation of next-generation batteries requires the development of safe, compatible electrolytes that are stable and do not cause safety problems. The difluoro(oxalato)borate ([DFOB]⁻) anion has been used as an electrolyte additive to aid with stability, but such an approach has most commonly been carried out using flammable solvent electrolytes. As an alternative approach, utilisation of the [DFOB]⁻ anion to make ionic liquids (ILs) or Organic Ionic Plastic Crystals (OIPCs) allows the advantageous properties of ILs or OIPCs, such as higher thermal stability and non-volatility, combined with the benefits of the [DFOB]⁻ anion. Here, we report the synthesis of new [DFOB]⁻-based ILs paired with triethylmethylphosphonium [P₁₂₂₂]⁺, and diethylisobutylmethylphosphonium [P_122i4]⁺. We also report the first OIPCs containing the [DFOB]⁻ anion, formed by combination with the 1-ethyl-1-methylpyrrolidinium [C₂mpyr]⁺ cation, and the triethylmethylammonium [N₁₂₂₂]⁺ cation. The traditional synthetic route using halide starting materials has been successfully replaced by a halide-free tosylate-based synthetic route that is advantageous for a purer, halide free product. The synthesised [DFOB]⁻-based salts exhibit good thermal stability, while the ILs display relatively high ionic conductivity. Thus, the new [DFOB]⁻-based electrolytes show promise for further investigation as battery electrolytes both in liquid and solid-state form.     

Polyphosphazene Based Star‐Branched and Dendritic Molecular Brushes

A new synthetic procedure is described for the preparation of poly(organo)phosphazenes with star‐branched and star dendritic molecular brush type structures, thus describing the first time it has been possible to prepare controlled, highly branched architectures for this type of polymer. Furthermore, as a result of the extremely high‐arm density generated by the phosphazene repeat unit, the second‐generation structures represent quite unique architectures for any type of polymer. Using two relativity straight forward iterative syntheses it is possible to prepare globular highly branched polymers with up to 30 000 functional end groups, while keeping relatively narrow polydispersities (1.2–1.6). Phosphine mediated polymerization of chlorophosphoranimine is first used to prepare three‐arm star polymers. Subsequent substitution with diphenylphosphine moieties gives poly(organo)phosphazenes to function as multifunctional macroinitiators for the growth of a second generation of polyphosphazene arms. Macrosubstitution with Jeffamine oligomers gives a series of large, water soluble branched macromolecules with high‐arm density and hydrodynamic diameters between 10 and 70 nm.

     

The evolution of subcritical Achlioptas processes

In Achlioptas processes, starting from an empty graph, in each step two potential edges are chosen uniformly at random, and using some rule one of them is selected and added to the evolving graph. AlthouSgh the evolution of such ‘local’ modifications of the Erd?s–Rényi random graph process has received considerable attention during the last decade, so far only rather simple rules are well understood. Indeed, the main focus has been on ‘bounded‐size’ rules, where all component sizes larger than some constant B are treated the same way, and for more complex rules very few rigorous results are known. In this paper we study Achlioptas processes given by (unbounded) size rules such as the sum and product rules. Using a variant of the neighbourhood exploration process and branching process arguments, we show that certain key statistics are tightly concentrated at least until the susceptibility (the expected size of the component containing a randomly chosen vertex) diverges. Our convergence result is most likely best possible for certain generalized Achlioptas processes: in the later evolution the number of vertices in small components may not be concentrated. Furthermore, we believe that for a large class of rules the critical time where the susceptibility ‘blows up’ coincides with the percolation threshold. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 47, 174–203, 2015     

The Janson inequalities for general up‐sets

Janson and Janson, ?uczak and Ruciński proved several inequalities for the lower tail of the distribution of the number of events that hold, when all the events are up‐sets (increasing events) of a special form—each event is the intersection of some subset of a single set of independent events (i.e., a principal up‐set). We show that these inequalities in fact hold for arbitrary up‐sets, by modifying existing proofs to use only positive correlation, avoiding the need to assume positive correlation conditioned on one of the events. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 391–395, 2015     

A general hilbert space approach to wavelets and its application in geopotential determination

A general approach to wavelets is presented within a framework of a separable functional Hilbert space H. Basic tool is the construction of H-product kernels by use of Fourier analysis with respect to an orthonormal basis in H. Scaling functions and wavelet are defined in terms of H-product kernels. Wavelts are shown to be ‘building blocks’ that decorrelate the data. A pyramid scheme provides fast computation. Finally, the determination of the earth's gravitational potential from single and multipole expressions is organzied as an example of wavelet approximation in Hilbert space structure.     

Properties of nanometric and micrometric multilayered films made of three conducting polymers

The electrochemical, electrical and morphological properties of multilayered films formed by alternated layers of poly(3,4-ethylenedioxythiophene), polypyrrole, and poly[N-(2-cyanoethyl)pyrrole], which were prepared by electrochemical layer-by-layer deposition, have been investigated and compared with those of multilayered films formed by two conducting polymers. Results indicate that the electrochemical behavior of the films formed by three conducting polymers depends on the micrometric or nanometric thickness of the layers. Thus, the electroactivity increases until the thickness of these films reaches a threshold value (∼2 μm), while the electrostability of the films is very remarkable when their thickness is close to ∼4 μm or higher. On the other hand, comparison between multilayered systems made of two and three conducting polymers indicates that the third component introduces heterogeneity in the interfaces between consecutive layers, reducing the ability to store charge. Among the latter, multilayered films formed by poly(3,4-ethylenedioxythiophene) and polypyrrole have been found to be particularly electroactive and electrostable. The surface morphology and topography of the layers have been used to rationalize the electrochemical properties of the different materials.