Coumarin synthesis on π-acidic surfaces

Catalysis with anion–π interactions is emerging as an important topic in supramolecular chemistry. Among the reactions explored so far on π-acidic surfaces, coumarin synthesis stands out as a cascade process with several coupled anionic transition states. Increasing π-acidity has been shown in a different context to increase transition-state stabilisation and thus catalytic activity. In this report, we explore the possible use of macrocycles to accelerate coumarin synthesis between two π-acidic surfaces. To our disappointment, we found that compared to monomeric π-acids, coumarin synthesis within divalent macrocycles is clearly slower. Hindered access to an overly confined active site within the macrocycles could possibly account for this loss in activity, but several other explanations are certainly possible. However, operational coumarin synthesis on monomeric π-acidic surfaces is shown to tolerate structural modifications. Best results are obtained with structures that aim for proximity without obstructing transition-state stabilisation on the π-acidic surface.     

Carbazoles from the [4C+2C] Reaction of 2,3‐Allenols with Indoles

A mild and efficient method using readily available 1‐aryl‐2,3‐allenols and unprotected‐N indoles, Au⁺‐catalyzed cyclization, and aromatization to afford the final [4C+2C] products, carbazoles 4, with an excellent selectivity, is reported. The reaction demonstrates excellent regioselectivity and allows the N?H unit to undergo reactivity unprotected. A mechanism involving a spiropolycyclic intermediate has been proposed and synthetic application is also demonstrated.     

Self-assembled structures of 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol in hydrophobic polymer matrices prepared using different heat treatments

Journal of Nanoparticle Research - Ni-doped (CeO2?δ )–YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been...     

紧黎曼流形上的椭圆边界值问题

讨论一类非齐次非线性椭圆边界值问题.利用极大值原理证明了该问题解的梯度估计.作为它的应用得到了解的效率比估计.     

Modified Lagrangian vortex method with improved boundary conditions for water waves past a thin bottom‐standing barrier

Herein, the modified Lagrangian vortex method (LVM), a hybrid analytical‐numerical algorithm per se, is devised to simulate the process of vortex formation and shedding from the sharp edge of a zero‐thickness vertical plate under linear water‐wave attack. Application of the Helmholtz decomposition facilitates a convenient switch between the inviscid‐ and viscous‐flow models, thereby enabling easy incorporation of vorticity effects into the potential‐flow calculations for the viscous‐dominated region. In evaluating the potential‐flow component, making good use of the quickly convergent technique with singular basis functions, correctly capturing the singular behavior in velocity fields near the tip of the plate, leads to a considerable reduction of computational burdens and to 12‐decimal‐place accuracy. The viscous correction is carried out via the meshless LVM with improved boundary conditions. Comparisons with previously published results show good agreement. Simulations of vortex generation and evolution illuminate the ability of the present method, and provide a supplement to pertinent experimental works. The hybrid scheme proposed herein allows flexibility for the former LVM and convenience in the code development. Such a compromise fits particularly well for the high‐resolution modeling of sharp‐edged vortex shedding without heavy numerical developments. Copyright © 2014 John Wiley & Sons, Ltd.