Oxidative Transformations of Organic Compounds Mediated by Redox Molecular Sieves

Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.^[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O₂, H₂O₂, and RO₂H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted.     

The new frozen spin target at MAMI

The new frozen spin polarized target for experiments at the polarized beam of the real photon facility A2 of the MAMI accelerator is described. The A2-collaboration at the Mainz Microtron MAMI is measuring photon absorption cross section using circularly and linearly polarized photons up to the energy of 1.5 GeV. The photons are produced in the’ Bremsstrahlungs’ process. In the years 2005/2006 the Crystal Ball detector with its unique capability to cope with multi photon final states was set up in Mainz. Since 2010 the experimental apparatus has been completed by a polarized target. The horizontal dilution refrigerator of the Frozen-Spin Target has been constructed and is operated in close cooperation with the Joint Institute for Nuclear Research in Dubna, Russia. The system offers the opportunity to provide longitudinally and transversely polarized protons and deuteron. In this paper the operation experience of this new Frozen-Spin Target and first results from the runs in 2010 and 2011 are presented.     

Efficient immobilisation of Rh-MonoPhos on the aluminosilicate AlTUD-1

Rhodium-MonoPhos was successfully immobilised by ionic interactions on aluminosilicate AlTUD-1. The resulting new heterogeneous catalyst can be used in water and showed excellent enantioselectivity and activity in the asymmetric hydrogenation of methyl-2-acetamidoacrylate.     

First Measurement of the Gerasimov-Drell-Hearn Sum Rule for 1H from 0.7 to 1.8 GeV at ELSA

To verify the fundamental Gerasimov-Drell-Hearn (GDH) sum rule for the first time experimentally, we measured the helicity dependent total photoabsorption cross section with circularly polarized real photons and longitudinally polarized nucleons in the photon energy range 0.68-1.82 GeV with the tagged photon facility at ELSA. The experiment was carried out with a 4pi detection system, a circularly polarized tagged photon beam, and a frozen spin polarized proton target. The contribution to the GDH sum rule in this photon energy range is [49.9+/-2.4(stat)+/-2.2(syst)] microb.     

Copper(II)-catalysed aerobic oxidation of primary alcohols to aldehydes

[CuBr2(2,2'-bipyridine)] catalyses the selective and very mild aerobic oxidation of primary alcohols to aldehydes in acetonitrile:water (2:1) in the presence of 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) and a base as cocatalysts.     

Quorum sensing regulates electric current generation of Pseudomonas aeruginosa PA14 in bioelectrochemical systems

Here, we show that quorum sensing (QS) modulates the current generation of the anode-respiring bacterium Pseudomonas aeruginosa because it controls the production of phenazines, which mediate the electron transfer to the anode. The current generation by a wildtype (WT) strain P. aeruginosa PA14 and the GacS/GacA protein-regulatory mutant retS was investigated under different environmental conditions. The retS mutant generated significantly higher current (45-fold) than the WT under anaerobic conditions. Anaerobic current generation by the WT was 28-fold higher with extraneously supplied lactones (a QS-signaling molecule). Compared to anaerobic conditions, the WT with some oxygen (microaerobic conditions) exhibited enhanced phenazine production (39-fold) and current levels (48-fold). Iron-rich medium and microaerobic conditions had a negative impact on current generation by retS. All these results were directly linked to QS activity in P. aeruginosa, thus, demonstrating the importance of this bacterial communication system for current generation in BESs. We also show that BESs represent a new tool for real-time investigation of phenazine-related QS activity.     

Measurement of the G asymmetry for the γp↦Nπ channels in the Δ(1232) resonance region

The G asymmetry of the γp↦Nπ reaction has been measured for the first time for E_γ = 340±14 MeV. This observable, for which very scarce published data exist, plays an important role to disentangle the contributions of the various nucleon resonances. The experiment, performed at the Mainz microtron MAMI, used a 4π-detector system, a linearly polarized, tagged photon beam, and a longitudinally polarized proton target.     

Photoproduction of positive pions from hydrogen with PHOENICS at ELSA

The differential cross section of the reaction γp→π⁺n has been measured with the PHOENICS detector at ELSA in Bonn. For the first time this cross section has been determined simultaneously over a large range of photon energies (E_γ = 220−900 MeV) and pion angles (Θ^c.m._pi = 35°−135°) with a tagged photon facility. The experimental set-up allowed a considerable kinematic overdetermination of the investigated reaction. Accordingly, the background contributions have been suppressed to below 1%. The measured differential cross section is in good agreement with existing data. The comparison with different model calculations is presented.