Synthesis of chiral allenes from ynamides through a highly stereoselective Saucy-Marbet rearrangement

A highly stereoselective Saucy-Marbet rearrangement using chiral ynamides and propargyl alcohols is described here. This rearrangement can be catalyzed by para-nitrobenzenesulfonic acid and leads to high diastereoselectivities for a range of different chiral propargyl alcohols and ynamides in a stereochemically intriguing matched, mismatched or indifferent manner. The stereoselective Saucy-Marbet rearrangement of ynamides provides an excellent entry to highly substituted chiral homo allenyl alcohols.     

Copper sulfate-pentahydrate-1,10-phenanthroline catalyzed amidations of alkynyl bromides. Synthesis of heteroaromatic amine substituted ynamides

A practical cross-coupling of amides with alkynyl bromides using catalytic CuSO(4).5H(2)O and 1,10-phenanthroline is described here. This catalytic protocol is more environmentally friendly than the use of CuCN or copper halides and provides a general entry for syntheses of ynamides including various new sulfonyl and heteroaromatic amine substituted ynamides. Given the interest in ynamides, this N-alkynylation of amides should be significant for the future of ynamides in organic synthesis.     

Interaction of electronic structure and nuclear dynamics on the S1 reaction surface for the ring opening of cyclohexadiene

For the ultrafast photoinduced ring opening of cyclohexadiene the S₁ state plays a central role, providing the possibility to rapidly decay to the ground state. In this paper we follow the path of a wavepacket propagating in the reactive coordinate space of the S₁ surface. We present a detailed analysis of the corresponding electronic and nuclear motions. With the help of a projection method and a normal-mode analysis, the vibrational modes driving the reaction might be detected experimentally. Received: 10 November 1999 / Published online: 13 July 2000     

Strong Metal–Support Interactions between Copper and Iron Oxide during the High‐Temperature Water‐Gas Shift Reaction

The commercial high‐temperature water‐gas shift (HT‐WGS) catalyst consists of CuO‐Cr₂O₃‐Fe₂O₃, where Cu functions as a chemical promoter to increase the catalytic activity, but its promotion mechanism is poorly understood. In this work, a series of iron‐based model catalysts were investigated with in situ or pseudo in situ characterization, steady‐state WGS reaction, and density function theory (DFT) calculations. For the first time, a strong metal‐support interaction (SMSI) between Cu and FeO_x was directly observed. During the WGS reaction, a thin FeO_x overlayer migrates onto the metallic Cu particles, creating a hybrid surface structure with Cu‐FeO_x interfaces. The synergistic interaction between Cu and FeO_x not only stabilizes the Cu clusters, but also provides new catalytic active sites that facilitate CO adsorption, H₂O dissociation, and WGS reaction. These new fundamental insights can potentially guide the rational design of improved iron‐based HT‐WGS catalysts.     

Acoustic timescale characterisation of a one-dimensional model hot spot

Hot spots have been shown to be the autoignition centre in reactive mixtures. Linear temperature gradients and thermal stratification are used to characterise their behaviour. In this work, a model hot spot is considered by combining a linear temperature gradient with a constant temperature plateau. This approach retains the simplicity of a linear temperature gradient, but captures the effects of a local temperature maximum of finite size. A one-step Arrhenius reaction for H₂–air is used to model the reactive mixture. Plateaus of three different initial sizes spanning two orders of magnitude are simulated. Each length corresponds to a different ratio of excitation time to acoustic time. It is shown that ratios less than unity react at nearly isochoric conditions while ratios greater than unity react at nearly isobaric conditions. Furthermore, it is demonstrated that the gasdynamic response is characterised by the a priori prescribed hot spot acoustic timescale ratio. Based upon the prescribed timescale ratio, it is shown that the plateau can have either a substantial or negligible impact on the reaction of a surrounding temperature gradient. This is explored further as the slope of the temperature gradient is varied. Based upon the heating-to-acoustic timescale ratio, plateaus of a particular size are shown to facilitate detonation formation inside gradients that would otherwise not detonate.     

Specific heat of superconducting Zn nanowires

We present heat capacity measurements on crystalline Zn nanowires with diameters of 230 and 23 nm, bracketing the superconducting coherence length of 155 nm. Transport measurements on superconducting nanowires have found a crossover from three-dimensional to one-dimensional behavior as the wire diameter was reduced below the coherence length. In contrast, the normalized heat capacity peak of the 23 nm Zn nanowires is found to be nearly identical to that of 230 nm wires and bulk Zn, indicating their thermodynamic properties remain three dimensional.