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By resorting to the principle of remote activation, we herein demonstrate the first photoredox catalyzed (3+3) dipolar cycloaddition of nitrones with aryl cyclopropanes. Key to the fidelity of the reaction resides in a facile manner of substrate activation by single‐electron transfer (SET) oxidation with photoredox catalysis, and the reaction takes place through a stepwise cascade encompassing a three‐electron‐type nucleophilic substitution triggered cyclopropane ring‐opening and a diastereoselective 6‐endo‐trig radical cyclization manifold. The reaction proceeds under mild conditions with excellent regio‐ and stereoselectivity, nicely complementing the well‐developed Lewis acid catalyzed cycloaddition of donor‐acceptor cyclopropanes. Other merits of the protocol include wide scope of aryl cyclopropanes with diversified substitution patterns and good functional‐group compatibility. A mechanism involving an aryl radical cation promoted remote activation mode was also proposed and supported by mechanistic experiments. [ABSTRACT FROM AUTHOR]

Mn and Na additives have been widely studied to improve the efficiency of CO2 hydrogenation to valuable olefins on Fe catalysts, but their effects on the catalytic properties and mechanism are still under vigorous debate. This study shows that Fe‐based catalysts with moderate Mn and Na contents are highly selective for CO2 hydrogenation to olefins, together with low selectivities for both CO and CH4 and much improved space‐time olefin yields compared to state‐of‐the‐art catalysts. Combined kinetic assessment and quasi in situ characterizations further unveil that the sole presence of Mn suppresses the activity of Fe catalysts because of the close contact between Fe and Mn, whereas the introduction of Na mediates the Fe–Mn interaction and provides strong basic sites. This subtle synergy between Na and Mn sheds light on the importance of the interplay of multiple additives that could bring an enabling strategy to improve catalytic activity and selectivity. [ABSTRACT FROM AUTHOR]

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO2) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO2) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. [ABSTRACT FROM AUTHOR]

The photoinduced regio- and enantioselective coupling of naphthols and derivatives thereof is achieved in the confined chiral coordination space of a RuII metalloligand based cage. The racemic or enantiopure cages encapsulate naphthol guests, which then undergo a regiospecific 1,4-coupling, rather than the normal 1,1-coupling, to form 4-(2-hydroxy-1-naphthyl)-1,2-napthoquinones; moderate stereochemical control is achieved with homochiral cages. The photoreactions proceed under both aerobic and anaerobic conditions but through distinct pathways that nevertheless involve the same radical intermediates. This unusual dimerization constitutes a very rare example of asymmetric induction in biaryl coupling by making use of coordination cages with dual functionality-photoredox reactivity and stereoselectivity. [ABSTRACT FROM AUTHOR]

Cyclobutane und Cyclobutene sind wichtige Strukturmotive, die in zahlreichen biologisch bedeutenden Verbindungen vorkommen, und nützliche Zwischenstufen in der chemischen Synthese. Entsprechend haben sich [2+2] ‐ Cycloadditionen zur Synthese von Cyclobutanen und Cyclobutenen als besonders nützliche Umwandlungen erwiesen. In den letzten 10 Jahren ist die Zahl der Publikationen zu katalytischen enantioselektiven [2+2] ‐ Cycloadditionen gestiegen. Diese Reaktionen machen eine Vielzahl zuvor nicht erhältlicher enantiomerenangereicherter chemischer Verbindungen zugänglich. In diesem Kurzaufsatz wird über die Fortschritte bei katalytischen enantioselektiven [2+2] ‐ Cycloadditionen für die Synthese von Cyclobutanen und Cyclobutenen berichtet. Gesteuertes Quadrat: Cyclobutane und Cyclobutene sind wichtige Strukturmotive in zahlreichen biologisch bedeutenden Verbindungen und nützliche Zwischenstufen in der chemischen Synthese. Demzufolge entwickelten sich katalytische enantioselektive [2+2] ‐ Cycloadditionen als interessante Methode zur Herstellung von Cyclobutanen und Cyclobutenen. Der Kurzaufsatz beschreibt die Fortschritte bei katalytischen enantioselektiven [2+2] ‐ Cycloadditionen. [ABSTRACT FROM AUTHOR]

Carbonate hydrogenation to formate is a promising route to convert captured carbon dioxide into valuable chemicals, thus reducing carbon emissions and creating a revenue return. Developing inexpensive catalysts with high activity, selectivity, and stability remains challenging. We report a supported non‐noble metal catalyst, Ni/TiO2, with great selectivity over 96 % and excellent stability in catalyzing the conversion of carbonate into formate in aqueous solution. Ni0 and Ni2+ species are both observed in Ni/TiO2 catalysts, and the synergistic effect of these two Ni components leads to high activity and high selectivity of carbonate hydrogenation to formate. [ABSTRACT FROM AUTHOR]

Orsellinic acid (OA) derivatives are produced by filamentous fungi using nonreducing polyketide synthases (nrPKSs). The chain‐releasing thioesterase (TE) domains of such nrPKSs were proposed to also catalyze dimerization to yield didepsides, such as lecanoric acid. Here, we use combinatorial domain exchanges, domain dissections and reconstitutions to reveal that the TE domain of the lecanoric acid synthase Preu6 of Preussia isomera must collaborate with the starter acyl transferase (SAT) domain from the same nrPKS. We show that artificial SAT‐TE fusion proteins are highly effective catalysts and reprogram the ketide homologation chassis to form didepsides. We also demonstrate that dissected SAT and TE domains of Preu6 physically interact, and SAT and TE domains of OA‐synthesizing nrPKSs may co‐evolve. Our work highlights an unexpected domain–domain interaction in nrPKSs that must be considered for the combinatorial biosynthesis of unnatural didepsides, depsidones, and diphenyl ethers. [ABSTRACT FROM AUTHOR]

Direct conversion of methane into value‐added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO2 suspended in an aqueous solution was used for the oxidation of methane to methanol. Promoted by copper cations (as co‐catalyst) in solution, the catalysts exhibited high activity and selectivity for the production of methanol using molecular oxygen with the presence of carbon monoxide at 150 °C with a reaction pressure of 31 bar. Millimole level yields of methanol were reached with the selectivity higher than 99 % using the Rh/TiO2 catalysts with the promotion of the copper cation. CO was the reductive agent to generate H2 from H2O, which led to the formation of H2O2 through the reaction of H2 and O2. Atomically dispersed Rh activated the C−H bond in CH4 and catalyzed the oxidation using H2O2. Copper cations maintained the low‐valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol. [ABSTRACT FROM AUTHOR]

Even though the diagnostic and prognostic value of circulating tumor cells (CTCs) has been demonstrated, their clinical utility and widespread adoption have been limited. Herein, we describe a new device, size-dictated immunocapture chip (SDI-Chip), for efficient, sensitive, and spatially resolved capture and detection of CTCs. SDI-Chip enables selective, frequent, and extended interaction of CTCs with hydrodynamically optimized immunocoated micropillar surfaces. CTCs with different antigen expression levels can be efficiently captured and spatially resolved around the micropillars. Capture efficiency greater than 92 % with a purity of 82 % was achieved with blood samples. CTCs were detected in non-metastasis colorectal (CRC) patients, while none was detected from healthy volunteers. We believe that SDI-Chip will facilitate the transition of tumor diagnosis from anatomical pathology to molecular pathology in localized CRC patients. [ABSTRACT FROM AUTHOR]