Rhodium-catalyzed reductive aldol reactions using aldehydes as the stoichiometric reductants

Chelated acyl rhodium hydrides, generated from the addition of [Rh(dppe)]ClO4 to beta-sulfide-substituted aldehydes, can function as the stoichiometric reductants in reductive aldol processes. Unsaturated nitriles, esters, and ketones can be used as enolate equivalents, and a variety of simple alpha- and beta-substituted aldehydes can be employed. The use of a second, more electrophilic, aldehyde allows three-component reactions to be performed.     

A recycling technique for the chromatographic separation of enantiomers and diastereomers on triacetylcellulose

A simple and inexpensive equipment for the optical resolution of enantiomers (and separation of diastereomers) on triacetylcellulose in ethanol at elevated pressure is described. It involves a closed circuit of solvent (pump—column—detector—pump) allowing a continuous chromatography up to 16 cycles without stopping the flow or handling fractions.This useful and versatile method permitting also the determination of enantiomeric purities is illustrated by several examples of centro-, axial- and planarchiral arenes and metallocenes.Herrn Prof. Dr.U. Schmidt, Stuttgart, zum 60. Geburtstag gewidmet.     

Fluordiazadiphosphetidine, 3. Mitt.: Die thermische Behandlung von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2,4-diazadiphosphetidin unter Druck in Gegenwart von Phosphor(V)fluorid und Alkalimetallfluoriden

Prolonged heating of (CH₃NPF₃)₂ in a sealed tube at 120°C yields (CH₃N)₄P₃F₇ and PF₅. Under the experimental conditions these compounds react to (CH₃N)₄P₃F₆ ⁺PF₆ ^–. Reaction of (CH₃NPF₃)₂ in the presence of PF₅ leads to a marked decrease in the formation of the ionic compound. The influence of the fluoride donating saltsMF (M=Li, Na, K, Cs) is investigated.

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Früher: Alkyliminophosphorsäuretrihalogenide, 1. und 2. Mitt.     

Analysis of cyanobacterial toxins by hydrophilic interaction liquid chromatography-mass spectrometry

The combination of hydrophilic interaction liquid chromatography with electrospray mass spectrometry (HILIC-MS) has been investigated as a tool for the analysis of assorted toxins produced by cyanobacteria. Toxins examined included saxitoxin and its various analogues (1-18), anatoxin-a (ATX-a, 19), cylindrospermopsin (CYN, 20), deoxycylindrospermopsin (doCYN, 21), and microcystins-LR (22) and -RR (23). The saxitoxins could be unequivocally detected in one isocratic analysis using a TSK gel Amide-80 column eluted with 65% B, where eluent A is water and B is a 95% acetonitrile/water solution, both containing 2.0 mM ammonium formate and 3.6 mM formic acid. The analysis of ATX-a, CYN and doCYN required 75% B isocratic. Simultaneous determination of 1-21 was also possible by using gradient elution. HILIC proved to be suitable for the analysis of microcystins, but peak shape was not symmetric and it was concluded that these compounds are best analysed using existing reversed-phase methods. The HILIC-MS method was applied to the analysis of field and cultured samples of Anabaena circinalis and Cylindrospermopsis raciborskii. In general, the method proved quite robust with similar results obtained in two different laboratories using different instrumentation.     

Synthesis and properties of new ditertiary stibines based upon o-, m- or p-xylyl and m- or p-phenylene backbones and their complexes with tungsten, iron and nickel carbonyls

High yield syntheses for 1,2-, 1,3-, and 1,4-xylyl distibines (1,2-C6H4(CH2SbMe2)2, 1,3-C6H4(CH2SbMe2)2, 1,4-C6H4(CH2SbMe2)2, respectively) from Me2SbCl (conveniently made in situ from Me2PhSb and HClgas) and the appropriate di-Grignard are reported. The 1,3- and 1,4-phenylene distibines, 1,3-C6H4(SbMe2)2 and 1,4-C6H4(SbMe2)2, were made similarly. The new ligands have been characterised by mass spectrometry, 1H and 13C[1H] NMR spectroscopy, and by the preparation of methiodide derivatives. The crystal structures of 1,4-C6H4(CH2SbMe2)2 and [1,3-C6H4(CH2SbMe3)2]I2 have been determined. The synthesis of 1,2-C6H4(CH2SbPh2)2 has been achieved similarly in modest yield and the distibine converted into the tetra-iodo-derivative 1,2-C6H4(CH2SbPh2I2)2. The coordination modes available to these ligands have been probed by the synthesis and characterisation of complexes with nickel, iron and tungsten carbonyls. The crystal structure of [[Fe(CO)4]2[micro-1,3-C6H4(CH2SbMe2)2]] has been determined. The spectroscopic properties of these carbonyl derivatives have been compared with those of complexes of other antimony ligands, and in some cases with diphosphine and diarsine complexes, to probe the electronic properties of the new ligands.     

Interpolation of diabatic potential energy surfaces

A method is presented for constructing diabatic potential energy matrices from ab initio quantum chemistry data. The method is similar to that reported previously for single adiabatic potential energy surfaces, but correctly accounts for the nuclear permutation symmetry of diabatic potential energy matrices and other complications that arise from the derivative coupling of electronic states. The method is tested by comparison with an analytic model for the two lowest energy states of H(3).     

(4+2)-cycloadditions of substituted arenediazocyanides: A kinetic study of a new dienophile

The rate constants of the (4+2)-cycloaddition reaction between substituted $\text{E}$-arenediazocyanides and 2,3-dimethyl-1,3-butadiene have been determined in several solvents. The reaction displays linear Hammett behavior; the data suggest a concerted reaction mechanism.     

Multilayer sol-gel membranes for optical sensing applications: single layer pH and dual layer CO(2) and NH(3) sensors

Organo-silica sol-gel membranes have been prepared and demonstrated in a single layer format for pH measurement and multiple-layer format for both carbon dioxide and ammonia. The sensors are simple and versatile since the same chemistry and membranes are used for each sensor. The sensors use hydroxypyrenetrisulfonic acid (HPTS) as the indicator immobilized in a base-catalyzed sol-gel containing poly(dimethyl)siloxane, aminopropyltriethoxysilane (APTES) and tetraethylorthosilicate (TEOS). This indicator gel is over coated with a hydrophobic sol-gel to reduce cross reactivity to pH when either CO(2) or NH(3) are examined. The gels are very stable and the sensors retain response up to a 12-month period. Sensors can be stored in buffer or dry without loss of function and have response times to that are comparable to literature values.     

The influence of pentaamminerhodium(III) on the1H n.m.r. spectra and pyrrole pKas of coordinated imidazoles and pyrazoles

Summary The following [(NH₃)₅RhLH]Cl₃ salts were preparedvia the [(NH₃)₅Rh(O₃SCF₃)](O₃SCF₃)₂ synthetic route; LH=1-methylimidazole (1CH₃imH), 2-methylimidazole (2CH₃imH), 4-methylimidazole (4CH₃imH), 5-methylimidazole(5CH₃imH), and pyrazole (pyzH). pK_a's at 25.0°C were determined for [(NH₃)₅RhLH]³⁺ complexes as follows: 2CH₃imH, 10.4±0.1; 5CH₃imH/4CH₃imH isomer mixture, 10.3±0.1; pyzH, 6.54±0.05. The influence on the pK_a's of imidazoles is dominated by withdrawal of the rhodium(III) centre and may be compensated by the presence of ring methylation by only 0.5log units for cobalt(III) and rhodium(III) derivatives, compared to 1.3 units for the -withdrawing ruthenium(III) centre. In the case of the -acceptor pyrazole ring, [(NH₃)₅Rh]³⁺ is observed to serve as a slight -donor and raises the pK_a above the cobalt(III) analogue. The¹H n.m.r. spectra of [(NH₃)₅RhLH]³⁺ complexes of the substituted imidazoles and pyrazole exhibit a deshielding order. C–2H>C–5H>C–4H for imidazoles and C–3H>C–5H>C–4H for pyrazole, as do their cobalt(III) analogues. The magnitude of values (=_{free L}-_complex) are virtually the same as in the cobalt(III) systems which shows that TIP influences are unimportant compared to ring rehybridization in estabilishing chemical shifts for both the cobalt(III) and rhodium(III) complexes. The imidazolato and pyrazolato complexes exhibit resonances upfield of the respective substituted imidazole or pyrazole complex in keeping with more negative charge on the rings; the influence is largest at C–2H of imidazolates and C–3H of pyrazolate.     

A critical comparison of approximation methods and models for equilibrium properties of low-barrier hydrogen bonds

Recent experimental evidence has led to the conclusion that short, strong hydrogen bonds can stabilize transition states of enzyme catalyzed biochemical reactions. Evidence for such hydrogen bonds is the low value of the isotopic fractionation factor, phi, which is defined as the equilibrium constant for the generic reaction, R-H + DOH <--> R-D + HOH, where H is the hydrogen atom participating in the low-barrier hydrogen bond in a molecule R-H. In this work we assess two approximation methods for computing the isotopic fractionation factors for single and multidimensional systems containing a low-barrier hydrogen bond. These methods are WKB and an approach that corrects the classical partition function via a quantum correction factor. We find that the latter approach is universally accurate and applicable in both single and multidimensional systems containing a low-barrier hydrogen bond. We also assess two different models for the coupling of a molecule's low-barrier hydrogen bond to other degrees of freedom, both internal and external to the molecule, and show that each leads to a lowering of the fractionation factor.