In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C −C Stille Coupling

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.     

Performing solvation free energy calculations in LAMMPS using the decoupling approach

Journal of Computer-Aided Molecular Design - The decoupling approach to solvation free energy calculations requires scaling the interactions between the solute and the solution with all...     

Asymmetric Carboxycyanation of Aldehydes by Cooperative AlF/Onium Salt Catalysts: from Cyanoformate to KCN as Cyanide Source

Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 10⁴. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results.     

Detection challenges in quantitative polymer analysis by liquid chromatography

Accurate quantification of polymer distributions is one of the main challenges in polymer analysis by liquid chromatography. The response of contemporary detectors is typically influenced by compositional features such as molecular weight, chain composition, end groups, and branching. This renders the accurate quantification of complex polymers of which there are no standards available, extremely challenging. Moreover, any (programmed) change in mobile‐phase composition may further limit the applicability of detection techniques. Current methods often rely on refractive index detection, which is not accurate when dealing with complex samples as the refractive‐index increment is often unknown. We review current and emerging detection methods in liquid chromatography with the aim of identifying detectors, which can be applied to the quantitative analysis of complex polymers.     

Degradation of a polyester‐urethane coating: Physical properties

In this article we studied the evolution of thermomechanical properties of a polyester‐urethane coating during degradation under different degradation conditions, i.e., aerobic and anaerobic conditions with and without dry/wet cycling during degradation. Dynamic mechanical and thermal analyses show that under aerobic conditions the coatings become stiffer and more brittle in the glassy state. This stiffening is probably due to the increase in the amount of hydrogen bonding and the formation of oxidized groups which increase the polarity of the material and enhance the interactions of the polymer segments. However, oxidation reactions result in a considerable decrease in cross‐link density and stiffness in the rubbery state. Both changes, in the glassy and rubbery states, give rise to development of internal stresses. These stresses increase as the degradation process proceeds. Nevertheless, for samples exposed to anaerobic conditions, the stiffness remains constant in the glassy state and the cross‐link density slightly increases as a result of degradation. This reconfirms the dominance of the effect of oxidation reactions on the mechanical failure of the coatings. Oxygen permeation measurements show a more‐or‐less time‐independent diffusion coefficient and a gradual decrease in solubility of oxygen as a function of exposure time. This results in a slight decrease in oxygen permeation (mainly in the early stage of the degradation) as degradation proceeds. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 659–671     

Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates

The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β‐ and γ‐aminoalcohols as well as α‐ and β‐aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N‐tosylisocyanate in a single step into highly enantioenriched N‐tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation‐induced [3,3]‐rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl‐protected allylic amines, which can be deprotected under non‐reductive conditions.     

Optimal Exercise Strategies for Operational Risk Insurance via Multiple Stopping Times

In this paper we demonstrate how to develop analytic closed form solutions to optimal multiple stopping time problems arising in the setting in which the value function acts on a compound process that is modified by the actions taken at the stopping times. This class of problem is particularly relevant in insurance and risk management settings and we demonstrate this on an important application domain based on insurance strategies in Operational Risk management for financial institutions. In this area of risk management the most prevalent class of loss process models is the Loss Distribution Approach (LDA) framework which involves modelling annual losses via a compound process. Given an LDA model framework, we consider Operational Risk insurance products that mitigate the risk for such loss processes and may reduce capital requirements. In particular, we consider insurance products that grant the policy holder the right to insure k of its annual Operational losses in a horizon of T years. We consider two insurance product structures and two general model settings, the first are families of relevant LDA loss models that we can obtain closed form optimal stopping rules for under each generic insurance mitigation structure and then secondly classes of LDA models for which we can develop closed form approximations of the optimal stopping rules. In particular, for losses following a compound Poisson process with jump size given by an Inverse-Gaussian distribution and two generic types of insurance mitigation, we are able to derive analytic expressions for the loss process modified by the insurance application, as well as closed form solutions for the optimal multiple stopping rules in discrete time (annually). When the combination of insurance mitigation and jump size distribution does not lead to tractable stopping rules we develop a principled class of closed form approximations to the optimal decision rule. These approximations are developed based on a class of orthogonal Askey polynomial series basis expansion representations of the annual loss compound process distribution and functions of this annual loss.