Nucleophilic displacements of non-racemic α-trifluoromethyl benzylic triflates

Effective protocols for the introduction of chiral α-trifluoromethyl benzyl moieties by nucleophilic displacement of enantiomerically enriched α-trifluoromethyl benzylic triflates are presented. The effects of substrate electronics, solvent polarity, temperature, and base are studied by measuring the diastereomeric or enantiomeric excesses of the displacement products formed by coupling a variety of α-trifluoromethyl benzylic triflates with a range of nucleophiles including amines, carboxylates, thiols, and malonates. Preliminary investigations to elucidate the mechanism(s) involved in the loss of stereochemical integrity at the benzylic center in the nucleophilic displacement reactions are also reported.     

Convexity Bias in Eurodollar Futures Prices: A Dimension-Free HJM Criterion

In the theory of interest rate futures, the difference between the futures rate and forward rate is called the “convexity bias,” and there are several widely offered reasons why the convexity bias should be positive. Nevertheless, it is not infrequent that the empirical the bias is observed to be negative. Moreover, in its most general form, the benchmark Heath–Jarrow–Morton (HJM) term structure model is agnostic on the question of the sign of the bias; it allows for models where the convexity bias can be positive or negative. In partial support of the practitioner’s arguments, we develop a simple scalar condition within the HJM framework that suffices to guarantee that the convexity bias is positive. Moreover, when we check this condition on the LIBOR futures data, we find strong empirical support for the new condition. The empirical validity of the sufficient condition and the periodic observation of negative bias, therefore leads one to a paradoxical situation where either (1) there are arbitrage possibilities or (2) a large subclass of HJM models provide interest rate dynamics that fail to capture a fundamental feature of LIBOR futures.     

Interfacial electronic structure of vanadyl naphthalocyanine on highly ordered pyrolytic graphite

We present a core and valence region spectroscopic analysis of the interfacial electronic structure of thin films of vanadyl naphthalocyanine (VONc) deposited onto highly oriented pyrolytic graphite (HOPG). X-ray photoelectron spectroscopy indicates the predominantly ionic character of the vanadyl metal center coordinated by the heterocycle and affords the bandgap in the thin VONc films. Valence band photoelectron spectroscopy points to the existence of three different adsorption geometries of VONc on the HOPG surface. The distribution of the different geometries can be systematically influenced in a simple post-deposition processing step, with an immediate effect on the interfacial electronic environment. We find spectroscopic evidence in the valence levels that VONc grows on HOPG most likely in a 2D-gas fashion rather than by nucleation and growth of islands. These data allow us to predict accurately the interface dipole in the case of a broad class of dipolar organic semiconductors, based simply on molecular dipole moment, polarizability and molecular diameter. This ability provides an important step towards rational optimization of energy level alignment in organic electronics.     

Quickest online selection of an increasing subsequence of specified size

Given a sequence of independent random variables with a common continuous distribution, we consider the online decision problem where one seeks to minimize the expected value of the time that is needed to complete the selection of a monotone increasing subsequence of a prespecified length n. This problem is dual to some online decision problems that have been considered earlier, and this dual problem has some notable advantages. In particular, the recursions and equations of optimality lead with relative ease to asymptotic formulas for mean and variance of the minimal selection time. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 49, 235–252, 2016     

Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).