A straightforward copper-free palladium methodology for the selective alkynylation of a wide variety of S-, O-, and N-based mono- and diheterocyclic bromides and chlorides

High-yield alkynylations are successfully achieved by a simple and widely accessible catalytic system for an unprecedented variety of heterocyclic bromides and chlorides in position -2, -3 or -5: pyridine, quinoline, thiophene, furan, thiazole, benzothiazole, pyrimidine, pyridazine, pyrazine, dioxepin halides are efficiently functionalized in short time reactions. This copper-free methodology employs 1 mol % palladium only, with inexpensive PPh₃ and amine base. The ionic liquid solvent allows a straigtforward separation of products and recycling opportunity. Unsuitable substrates and secondary reactions are also reported in order to point out further progress in cross-coupling using ionic liquids.     

Algorithms for propositional model counting

We present algorithms for the propositional model counting problem #SAT. The algorithms utilize tree decompositions of certain graphs associated with the given CNF formula; in particular we consider primal, dual, and incidence graphs. We describe the algorithms coherently for a direct comparison and with sufficient detail for making an actual implementation reasonably easy. We discuss several aspects of the algorithms including worst-case time and space requirements.     

Photo‐crosslinked fluorinated thin films from azido‐functionalized random copolymers

Random copolymers of styrene, p‐azidomethylstyrene and 1H,1H,2H,2H‐perfluorodecyl methacrylate were prepared in two steps involving nitroxide‐mediated radical copolymerization and azidation reaction and further characterized by ¹H and ¹⁹F NMR, size exclusion chromatography, differential scanning calorimetry, and thermal gravimetric analysis. Ultrathin films of these azidomethyl‐functionalized fluorinated random copolymers, with thicknesses ranging from 20 to 100 nm, were spin coated onto Si substrates and then crosslinked by ultraviolet irradiation resulting in smooth and insoluble crosslinked fluorinated polymer mats. The surface properties of the supported thin films were investigated by X‐ray photoelectron spectroscopy and water contact angle measurements. These tailored photo‐crosslinked coatings afford a versatile control and homogenization of the wetting properties of different organic and inorganic substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3888–3895, 2010     

Large time existence for 1D Green-Naghdi equations

We consider here the 1D Green-Naghdi equations that are commonly used in coastal oceanography to describe the propagation of large amplitude surface waves. We show that the solution of the Green-Naghdi equations can be constructed by a standard Picard iterative scheme so that there is no loss of regularity of the solution with respect to the initial condition.     

Soluble peptidyl phosphoranes for metal-free, stereoselective ligations in organic and aqueous solution

Protocols for solid-phase syntheses of soluble peptidyl phosphoranes are presented. Various supported phosphoranylidene acetates were prepared on Rink amide or via alkylation of trialkyl- and triarylphosphines with bromoacetyl Wang ester. C-Acylation was conducted racemization-free with activated Fmoc-amino acids, followed by SPPS (solid-phase peptide synthesis). Acidic conditions released decarboxylated peptidyl phosphoranes into solution. The protocol allowed for the electronic variation of peptidyl phosphoranes which were investigated in ligation reactions with azides in organic and aqueous solvents.     

On robust optimization of two-stage systems

Robust-optimization models belong to a special class of stochastic programs, where the traditional expected cost minimization objective is replaced by one that explicitly addresses cost variability. This paper explores robust optimization in the context of two-stage planning systems. We show that, under arbitrary measures for variability, the robust optimization approach might lead to suboptimal solutions to the second-stage planning problem. As a result, the variability of the second-stage costs may be underestimated, thereby defeating the intended purpose of the model. We propose sufficient conditions on the variability measure to remedy this problem. Under the proposed conditions, a robust optimization model can be efficiently solved using a variant of the L-shaped decomposition algorithm for traditional stochastic linear programs. We apply the proposed framework to standard stochastic-programming test problems and to an application that arises in auctioning excess electric power. Mathematics Subject Classification (1991):90C15, 90C33, 90B50, 90A09, 90A43Supported in part by NSF Grants DMI-0099726 and DMI-0133943     

An Efficient One-Pot Synthesis of Pyrazolopyrimidines, Intermediates for Potential Phosphodiesterase Inhibitors

A simple high-yielding procedure is presented for the synthesis of pyrazolopyrimidinones overcoming limitations found in earlier work and of considerable utility for the production of intermediates for potential phosphodiesterase inhibitors.     

Mild methods to assemble and pattern organic monolayers on hydrogen-terminated Si(111)

Mild methods to assemble well-ordered organic monolayers of olefins on Si(111) using 2,2,6,6-tetramethyl-1-piperidinyloxy and to pattern these monolayers on the micrometer-size scale using soft lithography are reported.     

Poly(arylene sulfide)s via nucleophilic aromatic substitution reactions of halogenated pyromellitic diimides

Nucleophilic aromatic substitution (SNAr) reactions are exploited to prepare poly(arylene sulfide)s (PAS's) via the reaction of bis-thiolates and dibrominated pyromellitic diimide (PMDI) derivatives. Small-molecule model studies reveal the reaction is well-defined and proceeds in quantitative yield in practical times at room temperature. Variation in comonomer feed ratios allowed some control over target polymer molecular weights in the step polymerization, but control was likely limited by the relatively poor polymer solubility in the dipolar aprotic solvents typically employed to promote SNAr reactions. One substitution pattern produces a steric “pocket” around the PMDI units, inducing a peculiar solubility trend in halogenated solvents; that is, greatly reduced solubility in CHCl₃ relative to CH₂Cl₂ and C₂H₂Cl₄. One example small-molecule readily dissolves in CHCl₃ at room temperature, then rapidly grows poorly soluble crystals revealed by single-crystal XRD to contain CHCl₃ molecules in the steric pockets. Finally, the recently demonstrated depolymerization of phthalonitrile-based PAS's via ipso substitution with monothiolates as chain scission agents yields quantitative molecular weight reduction to monomeric species from the polymers reported here.