Stereoselective Peterson Olefinations from Bench‐Stable Reagents and N‐Phenyl Imines

The synthesis of bench‐stable α,α‐bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ～1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N‐benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N‐bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained.     

DIFFERENTIAL-ALGEBRAIC APPROACH TO COUPLED PROBLEMS OF DYNAMIC THERMOELASTICITY

An efficient numerical approach for the general thermomechanical problems was developed and it was tested for a two-dimensional thermoelasticity problem. The main idea of our numerical method is based on the reduction procedure of the original system of PDEs describing coupled thermomechanical behavior to a system of Differential Algebraic Equations (DAEs) where the stress-strain relationships are treated as algebraic equations. The resulting system of DAEs was then solved with a Backward Differentiation Formula (BDF) using a fully implicit algorithm. The described procedure was explained in detail, and its effectiveness was demonstrated on the solution of a transient uncoupled thermoelastic problem, for which an analytical solution is known, as well as on a fully coupled problem in the two-dimensional case.     

Ring opening of cyclic N,O-acetals with allyltrimethylsilane under Lewis acidic conditions

Five and six-membered cyclic N,O-acetals with N-carboxyalkyl and sulfonyl groups undergo clean and high yielding ring opening with allyltrimethylsilane in the presence of strong Lewis acids to give homoallylic amine derivatives.     

Lessons for fragment library design: analysis of output from multiple screening campaigns

Over the past 8 years, we have developed, refined and applied a fragment based discovery approach to a range of protein targets. Here we report computational analyses of various aspects of our fragment library and the results obtained for fragment screening. We reinforce the finding of others that the experimentally observed hit rate for screening fragments can be related to a computationally defined druggability index for the target. In general, the physicochemical properties of the fragment hits display the same profile as the library, as is expected for a truly diverse library which probes the relevant chemical space. An analysis of the fragment hits against various protein classes has shown that the physicochemical properties of the fragments are complementary to the properties of the target binding site. The effectiveness of some fragments appears to be achieved by an appropriate mix of pharmacophore features and enhanced aromaticity, with hydrophobic interactions playing an important role. The analysis emphasizes that it is possible to identify small fragments that are specific for different binding sites. To conclude, we discuss how the results could inform further development and improvement of our fragment library. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

First passage time for multivariate jump‐diffusion processes in finance and other areas of applications

The first passage time (FPT) problem is an important problem with a wide range of applications in science, engineering, economics, and industry. Mathematically, such a problem can be reduced to estimating the probability of a stochastic process first to reach a boundary level. In most important applications in the financial industry, the FPT problem does not have an analytical solution and the development of efficient numerical methods becomes the only practical avenue for its solution. Most of our examples in this contribution are centered around the evaluation of default correlations in credit risk analysis, where we are concerned with the joint defaults of several correlated firms, the task that is reducible to a FPT problem. This task represents a great challenge for jump‐diffusion processes (JDP). In this contribution, we develop further our previous fast Monte Carlo method in the case of multivariate (and correlated) JDP. This generalization allows us, among other things, to evaluate the default events of several correlated assets based on a set of empirical data. The developed technique is an efficient tool for a number of financial, economic, and business applications, such as credit analysis, barrier option pricing, macroeconomic dynamics, and the evaluation of risk, as well as for a number of other areas of applications in science and engineering, where the FPT problem arises. Copyright © 2008 John Wiley & Sons, Ltd.     

Dual-parameter Correlation Analysis of the Fluorescence Data of 1-Methyl-2-formyl-5-substituted Pyrrole(4-nitrophenyl)hydrazones

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Structural characterization of silver dialkylphosphite salts using solid‐state 109Ag and 31P NMR spectroscopy,IR spectroscopy and DFT calculations

High‐resolution solid‐state ¹⁰⁹Ag and ³¹P NMR spectroscopy was used to investigate a series of silver dialkylphosphite salts, Ag(O)P(OR)₂ (R = CH₃, C₂H₅, C₄H₉ and C₈H₁₇), and determine whether they adopt keto, enol or dimer structures in the solid state. The silver chemical shift, CS, tensors and |J(¹⁰⁹Ag, ³¹P)| values for these salts were determined using ¹⁰⁹Ag (Ξ = 4.652%) NMR spectroscopy. The magnitudes of J(¹⁰⁹Ag, ³¹P) range from 1250 ± 10 to 1318 ± 10 Hz and are the largest reported so far. These values indicate that phosphorus is directly bonded to silver for all these salts and thus exclude the enol structure. All ³¹P NMR spectra exhibit splittings due to indirect spin–spin coupling to ¹⁰⁷Ag (I = 1/2, NA = 51.8%) and ¹⁰⁹Ag (I = 1/2, NA = 48.2%). The ¹J(¹⁰⁹Ag, ³¹P) values measured by both ¹⁰⁹Ag and ³¹P NMR spectroscopy agree within experimental error. Analysis of ³¹P NMR spectra of stationary samples for these salts allowed the determination of the phosphorus CS tensors. The absence of characteristic P?O stretching absorption bands near 1250 cm^?1 in the IR spectra for these salts exclude the simple keto tautomer. Thus, the combination of solid‐state NMR and IR results indicate that these silver dialkylphosphite salts probably have a dimer structure. Values of silver and phosphorus CS tensors as well as ¹J(¹⁰⁹Ag, ³¹P) values for a dimer model calculated using the density functional theory (DFT) method are in agreement with the experimental observations. Copyright © 2010 John Wiley & Sons, Ltd.