The Dihydropyrone Diels–Alder Reaction: Development and Application to the Synthesis of Highly Functionalized 1-Oxa-4-decalones

A facile method for the synthesis of highly functionalized 1-oxadecalone derivatives is described via the Diels–Alder reaction of 2,3-dihydro-4-pyrone dienophiles with electron rich dienes. By this process a variety of functional groups and substitution patterns can be incorporated into the oxadecalone framework.     

Gold‐Catalyzed Oxa‐Povarov Reactions for the Synthesis of Highly Substituted Dihydrobenzopyrans from Diaryloxymethylarenes and Olefins

Oxa‐Povarov reactions involving readily available diaryloxymethylarenes and aryl‐substituted alkenes are reported. Their [4+2] cycloadditions were efficiently catalyzed by IPrAuSbF₆ (IPr=1,3‐bis(diisopropylphenyl)imidazol‐2‐ylidene) with high diastereoselectivity. Product analysis revealed that the reactions likely proceed by a stepwise ionic mechanism, because both E‐ and Z‐configured β‐methylstyrene gave the same cycloadducts in the same proportions.     

The Interplay between Steric and Electronic Effects in SN2 Reactions

Myths of steric hindrance : In contrast with current opinion, energy decomposition analysis shows that the presence of bulky substituents at carbon leads to the release of steric repulsion in the transition state shown in the graphic. It is rather the weakening of the electrostatic attraction, and in particular the loss of attractive orbital interactions, that are responsible for the activation barrier.

     

Energetics of Formation of Cyclacenes from 2,3-Didehydroacenes and Implications for Astrochemistry

The carriers of the diffuse interstellar bands (DIBs) are still largely unknown although polycyclic aromatic hydrocarbons, carbon chains, and fullerenes are likely candidates. A recent analysis of the properties of n-acenes of general formula C_4n+2H_2n+4 suggested that these could be potential carriers of some DIBs. Dehydrogenation reactions of n-acenes after absorption of an interstellar UV photon may result in dehydroacenes. Here the reaction energies and barriers for formation of n-cyclacenes from 2,3-didehydroacenes (n-DDA) by intramolecular Diels–Alder reaction to dihydro-etheno-cyclacenes (n-DEC) followed by ejection of ethyne by retro-Diels–Alder reactions are analyzed using thermally assisted occupation density functional theory (TAO-DFT) for n=10–20. It is found that the barriers for each of the steps depend on the ring strain of the underlying n-cyclacene, and that the ring strain of n-DEC is about 75 % of that of the corresponding n-cyclacene. In each case, ethyne extrusion is the step with the highest energy barrier, but these barriers are smaller than CH bond dissociation energies, suggesting that formation of cyclacenes is an energetically conceivable fate of n-acenes after multiple absorption of UV photons.     

Combining Steric and Electrostatic Stabilization Using Hydrophilic MacroRAFT Agents in an Ab Initio Emulsion Polymerization of Styrene

Hydrophilic (co)polymers carrying a thiocarbonyl thio end group such as poly(dimethylaminoethyl methacrylate), poly(ethylene oxide), and poly(ethylene oxide)‐block‐poly(dimethylaminoethyl methacrylate) have been evaluated as precursors of stabilizers in batch ab initio emulsion polymerization of styrene under acidic conditions to form electrosterically stabilized polystyrene latex particles. As a mixture of P(DMAEMA/H⁺Cl⁻)‐RAFT and PEO‐RAFT failed to give satisfactory results, PEO‐RAFT was used as a control agent for the RAFT polymerization of DMAEMA, and the resulting block copolymer was successfully used in ab initio styrene emulsion polymerization.

     

FeNi Nanoparticles Coated on N-doped Ultrathin Graphene-like Nanosheets as Stable Bifunctional Catalyst for Zn-Air Batteries

High-performance and low-cost bifunctional catalysts are crucial to energy conversion and storage devices. Herein, a novel oxygen electrode catalyst with high oxygen evolution reaction and oxygen reduction reaction (OER/ORR) performance is reported based on bimetal FeNi nanoparticles anchored on N-doped graphene-like carbon (FeNi/N−C). The complete 2D ultrathin carbon nanosheet is induced by etching and stripping of molten sodium chloride and its ions in the carbonization process at suitable temperature. The obtained FeNi/N−C catalyst exhibits rapid reaction kinetics for OER, efficient four electron transfer for ORR, and outstanding bifunctional performance with reversible oxygen electrode index of 0.87 V for OER/ORR. Zn-air batteries with a high open-circuit voltage of 1.46 V and a stable discharge voltage of 1.23 V are assembled using liquid electrolytes, zinc sheet as Zn-electrode and FeNi/N−C coating on carbon cloth as air-electrode. The specific capacity is as high as 816 mAh g⁻¹ and there is extremely little decay after charge-discharge cycle time of 275 h for the FeNi/N−C as oxygen electrode catalyst in Zn-air battery, which are much better than that assembled with Pt/C−RuO₂ catalyst.     

Highly Ordered and Thermally Stable FeRh Cluster Superlattice on Graphene for Low-Temperature Catalytic CO Oxidation

We report on bimetallic FeRh clusters with a narrow size-distribution grown on graphene on Ir(111) as a carbon-supported model catalyst to promote low-temperature catalytic CO oxidation. By combining scanning tunneling microscopy with catalytic performance measurements, we reveal that Fe−Rh interfaces are active sites for oxygen activation and CO oxidation, especially at low temperatures. Rh core Fe shell clusters not only provide the active sites for the reaction, but also thermally stabilize surface Fe atoms towards coarsening compared with pure Fe clusters. Alternate isotope-labelled CO/O₂ pulse experiments show opposite trends on preferential oxidation (PROX) performance because of surface hydroxyl species formation and competitive adsorption between CO and O₂. The present results introduce a general strategy to stabilize metallic clusters and to reveal the reaction mechanisms on bimetallic structures for low-temperature catalytic CO oxidation as well as preferential oxidation.