Tandem Acid/Pd-Catalyzed Reductive Rearrangement of Glycol Derivatives

Herein, we describe the acid/Pd-tandem-catalyzed transformation of glycol derivatives into terminal formic esters. Mechanistic investigations show that the substrate undergoes rearrangement to an aldehyde under [1,2] hydrogen migration and cleavage of an oxygen-based leaving group. The leaving group is trapped as its formic ester, and the aldehyde is reduced and subsequently esterified to a formate. Whereas the rearrangement to the aldehyde is catalyzed by sulfonic acids, the reduction step requires a unique catalyst system comprising a Pd^II or Pd⁰ precursor in loadings as low as 0.75 mol % and α,α′-bis(di-tert-butylphosphino)-o-xylene as ligand. The reduction step makes use of formic acid as an easy-to-handle transfer reductant. The substrate scope of the transformation encompasses both aromatic and aliphatic substrates and a variety of leaving groups.     

Structural diversity within analogous compounds: syntheses and studies of M(SCH2CH2NH2)Cl (M = Zn, Cd, Hg)

The novel complexes [Zn(L)Cl] (1), [Cd(L)Cl] (2), [Hg(L)Cl] (3), {[Hg(L)Cl].NaOH.2H2O} (3.NaOH.2H2O), and {[Hg3(HL)2Cl6].2H2O} (4) (L = -SCH2CH2NH2) were prepared and investigated by means of IR spectroscopy and single-crystal X-ray diffraction. The crystal structures of 1, 2, and 3.NaOH.2H2O show chelating N,S-coordination of the cysteaminate ligand, bridging S, and terminally coordinating Cl. Apart from these common features, the coordination geometries and modes of intermolecular association are different. 1 forms a cyclic tetramer with a Zn4S4 ring, and 3.NaOH.2H2O contains one-dimensional [Hg(L)Cl]n chains with S-bridged Hg atoms. Zn and Hg atoms in 1 and 3.NaOH.2H2O are tetracoordinate with a distorted tetrahedral M(ClNS2) geometry (M = Zn, Hg). Each Cd atom of 2 binds to three S atoms and vice versa, such that layers of distorted Cd3S3 hexagons are formed. 2 is the first example for a compound exhibiting a group 12-group 16 layer structure, which can be described as an analogue of a graphite layer. Additionally, each Cd atom binds to a chlorine atom and a nitrogen atom from a cysteaminate ligand resulting in pentacoordination with a distorted trigonal bipyramidal Cd(ClNS3) geometry. 4 contains two differently coordinate Hg atoms. One displays a distorted trans-octahedral Hg(Cl4S2) geometry, while the other is coordinated by four Cl atoms and one S atom and additionally forms a long Hg...Cl contact.     

Development of a Ruthenium/Phosphite Catalyst System for Domino Hydroformylation–Reduction of Olefins with Carbon Dioxide

An efficient domino ruthenium‐catalyzed reverse water‐gas‐shift (RWGS)‐hydroformylation‐reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence.     

Restricted self-diffusion in an aqueous solution of poly(ethylene oxide) poly(propylene oxide) poly(ethylene oxide) triblock copolymer

 The self-diffusion behavior of a triblock copolymer (PEO–b– PPO–b–PEO) in an aqueous solution of 20% (m/m) was investigated during a temperature-induced phase transition from liquid to gel state using pulsed field gradient NMR and static light scattering. The measured self-diffusivity shows a strong dependence on the observation time in the gel phase indicating the existence of diffusion barriers in the size range of about 0.6 μm. Additional static light-scattering measurements show a structure in the same size range of several hundred nanometers, which is far above molecular or micellar sizes and thus, has to be caused by larger clusters. The similarity in the space scales suggests that the restriction of molecular propagation is correlated with the grain boundaries between the domains of the poly-crystalline structure formed by the arranged micelles. Received: 28 October 1996 Accepted: 21 March 1997     

Eich- und Standardisierungsprobleme in der HPLC

Zusammenfassung In der Praxis der Hochdruck-Flüssigkeits-Chromatographie muß der Analytiker möglichst genaue Resultate erhalten unter der Bedingung, daß der Zeit- und Arbeitsaufwand für die Eichung möglichst gering ist. Häufig sind die Komponenten einer Analyse nicht in einer Form erhältlich, die für Eichzwecke rein genug ist. Hier wird gezeigt, wie man unter gewissen Voraussetzungen dennoch die Eichfaktoren der reinen Komponenten bestimmen kann. Durch Sammeln und Auswerten von Faktorverhältnissen über einen längeren Zeitraum läßt sich der für die Eichung erforderliche Zeitaufwand wesentlich herabsetzen, wobei die Genauigkeit erhalten bleibt oder sogar verbessert wird. Dadurch, daß durchflußbereinigte Faktoren benutzt werden, kann dies noch weiter verbessert werden.

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On the problem of calibration and standardization in HPLC

Summary In practical high-pressure liquid chromatography the analyst must get results as accurate as possible under the condition that the amount of time and labour spent for calibration should be as low as possible. Often the components of the analysis are not available sufficiently pure for calibration purposes. It is shown here as under certain conditions the calibration factors of the pure components could be determined even with impure standard substances. By collecting and evaluating calibration factor ratios for a longer time, the time necessary for calibration could be reduced remarkably while maintaining or even improving the accuracy. This could be improved further by using factors which are flow-corrected.

     

The bulk dynamics of a compositionally asymmetric diblock copolymer studied using dynamic light scattering

We have studied the bulk dynamics of a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) (PEP-PDMS) diblock copolymer in a large temperature range both in the ordered and in the disordered state. The volume fraction of the PEP block is 0.22. Apart from the disordered state, the sample shows three ordered morphologies. Using dynamic light scattering, we have investigated the dynamics in all four phases and combined these results with those obtained using pulsed field gradient NMR. In the disordered state, we find--apart from the slow cluster mode--the heterogeneity mode related to the self-diffusion of single chains. The relaxation time of this mode, reduced by temperature and the zero-shear viscosity , , increases with temperature. In the cubic phase right below the ODT temperature, we observe two diffusive processes, and we attribute the faster one to the mutual diffusion of micelles and block copolymers not bound to micelles (“free chains”) through the PDMS matrix. The slower mode may either be due to the mutual diffusion of free chains and chains bound to PEP micelles or to the cooperative diffusion of micellar aggregates. In the non-cubic ordered state at intermediate temperatures, an additional weak diffusive mode is observed. The low-temperature ordered state is body-centered cubic, and here, only the mutual diffusion of micelles and free chains lies in our experimental time window. Received 19 March 1999 and Received in final form 25 August 1999     

B-->pipi, new physics in B-->piK, and implications for rare K and B decays

The measured B-->pipi,piK branching ratios (BRs) exhibit puzzling patterns. We point out that the B-->pipi hierarchy can be nicely accommodated in the standard model (SM) through nonfactorizable hadronic interference effects, whereas the B-->piK system may indicate new physics (NP) in the electroweak (EW) penguin sector. Using the B-->pipi data and the SU(3) flavor symmetry, we fix the hadronic B-->piK parameters and show that any currently observed feature of the B-->piK system can be easily explained through enhanced EW penguin diagrams with a large CP-violating NP phase. This in turn implies in particular an enhancement of the K(L)-->pi(0)nunu rate by 1 order of magnitude, with BR(K(L)-->pi(0)nunu) approximately 4BR(K+-->pi(+)nunu), BR(K(L)-->pi(0)e(+)e(-))=O(10(-10)), and (sin(2beta)(pinunu)<0. We address also other rare K and B decays and B(d)-->phiK(S).     

The $ B\to\pi K$ puzzle and its relation to rare B and K decays

The standard-model interpretation of the ratios of charged and neutral rates, R _c and R _n, respectively, points towards a puzzling picture. Since these observables are affected significantly by colour-allowed electroweak (EW) penguins, this puzzle could be a manifestation of new physics in the EW penguin sector. Performing the analysis in the R _n- R _c plane, which is very suitable for monitoring various effects, we demonstrate that we may, in fact, move straightforwardly to the experimental region in this plane through an enhancement of the relevant EW penguin parameter q. We derive analytical bounds for q in terms of a quantity L, which measures the violation of the Lipkin sum rule, and point out that strong phases around are favoured by the data, in contrast to QCD factorisation. The modes imply a correlation between q and the angle that, in the limit of negligible rescattering effects and colour-suppressed EW penguins, depends only on the value of L. Concentrating on a minimal flavour-violating new-physics scenario with enhanced Z ⁰ penguins, we find that the current experimental values on require roughly . As the data give , L has either to move to smaller values once the data improve or new sources of flavour and CP violation are needed. In turn, the enhanced values of L seen in the data could be accompanied by enhanced branching ratios for the rare decays , , and . Most interesting turns out to be the correlation between the modes and , with the latter depending approximately on a single scaling variable .Received: 8 September 2003, Published online: 12 November 2003