DMF promoted xylosylation of terpenols

The glycosidation of 2,3,4-triacetyl-1-bromo-α-d-xylopyranose with various terpenols occurs at 50 °C in DMF without the requirement of any additive. The decisive role of DMF as solvent on the coupling efficiency is highlighted.     

The cyano nitronyl nitroxide radical: experimental and theoretical evidence for the fourth case of the McConnell-I mechanism

The nitronyl nitroxide 2-cyano-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (1) crystallises in the tetragonal P42(1)m space group with a=7.4050(7), c=8.649(1) A. In the crystal the molecules form layers parallel to the ab plane in which they are orthogonal to each other. In the layers there are close contacts, 2.953(2) A, between the NO groups and the bridging carbon atoms of the O-N-C-N-O fragment of neighbouring radicals. The calculated spin density shows a positive population mainly and equally localised on the NO groups and small but significant negative spin densities on the bridging carbon atom and the cyano nitrogen. Absorption spectra show temperature-dependent transitions related to the magnetic behaviour. The temperature dependence of the magnetic susceptibility in the range 2-300 K reveals that couplings between the radicals are antiferromagnetic, and is interpreted by considering a two-dimensional square array of spin S=1/2 antiferromagnetically coupled (J=-10 cm(-1) and g=2.01). This is interpreted as an exchange coupling through close contact between positive and negative spin densities in orthogonal orbitals on oxygen and carbon atoms, respectively.     

Synthesis and complexing properties of a double-calix[4]arene crown ether

The template synthesis of copper(II) phthalocyanine by the condensation of dicyanobenzene within the supercages of Cu(II) exchanged X and Y type zeolites was studied using differential scanning calorimetry. The exotherms for intrazeolite and surface complexation have been resolved. These thermal events exhibit a dependence on the copper loading and hydration level which has been interpreted as a pressure effect.     

Asymmetric Synthesis of alpha-Amino Phosphonic Acids by Diastereoselective Addition of Trimethyl Phosphite onto Chiral Oxazolidines(1)

A simple and general asymmetric synthesis of alpha-amino phosphonic acids is described. The method involves the highly selective addition of trialkyl phosphite onto various chiral oxazolidines. Oxazaphosphorinanes thus obtained with an excellent diastereoselectivity furnish the corresponding (S)-alpha-substituted amino phosphonic acids in good overall yields and high ee (77-->97%) after simple deprotection.     

Polymer-supported approach for solution-phase synthesis of cysteine trap protease inhibitors: procedure for straightforward optimization of the P1-P1' pocket

Peptide-based reversible and irreversible cysteine proteases inhibitors are well reported in the literature. Many of these compounds have an electrophilic carbonyl group as a cysteine trap in the place of a scissile amide moiety of the natural substrate. As a common mechanism strategy, we have designed a probe library of a cysteine trap for rapid optimization of P1-P1' pockets of different cysteine proteases. The synthesis of this library using a straightforward methodology based on polymer-supported reagents and scavengers to avoid tedious purification steps has been achieved. For the selective monobromination of diazo ketones, preparation of a new supported reagent, piperidinoaminomethylpolystyrene hydrobromide, is also described.     

Biscarbene-ruthenium complexes in catalysis: novel stereoselective synthesis of (1E,3E)-1,4-disubstituted-1,3-dienes via head-to-head coupling of terminal alkynes and addition of carboxylic acids

The reaction of a variety of alkynes RCtbd1;CH with a variety of carboxylic acids R(1)CO(2)H, in the presence of 5% of RuCl(COD)C(5)Me(5), selectively leads to the dienylesters (1E,3E)-RCH(1)=CH(2)-CH(3)=C(R)(O(2)CR(1)). The reaction also applies to amino acid and dicarboxylic acid derivatives. It is shown that the first step of the reaction consists of the head-to-head alkyne coupling and of the formation of the metallacyclic biscarbene-ruthenium complex isolated for R = Ph and catalyzing the formation of dienylester. D-labeled reactions show that the alkyne protons remain at the alkyne terminal carbon atoms and carboxylic acid protonates the C(1) carbon atom. QM/MM (ONIOM) calculations, supporting a mixed Fischer-Schrock-type biscarbene complex, show that protonation occurs preferentially at the carbene carbon C(1) adjacent to Ru, in the relative cis position with respect to the Ru-Cl bond, to give a mixed C(1)alkyl-C(4)carbene complex in which the C(4) carbene is conjugated with the noncoordinated C(2)=C(3) double bond. This 16-electron intermediate has a weak stabilizing alpha agostic C-H bond. This most stable isomer appears to have a C(4) center more accessible to the nucleophilic addition which accounts for the experimentally observed product.     

Activity testing and surface characterization of pretreated fused-silica capillaries for gas chromatography A new modification of existing intermediate column tests

A new modification of existing intermediate capillary column tests for uncoated columns is presented. A short (1 m), thick film (2 μm) precolumn is coupled to the column to be tested. The use of a short precolumn results in a rapid test. This makes it attractive in terms of time to inject the test compounds separately, thus excluding mutual influences, in diluted solutions spiked with n-alkanes as references. Moreover, the short precolumn gives sharp Gaussian injection profiles on the second column. A simple versatile coupling device has been developed, which permits easy control and adjustment of pressures and carrier flows, monitoring of the effluents of the precolumn and introduction of sharp input bands on the second column. The monitor detector accurately shows the shape and time of introduction of the compounds on the second column. This permits the evaluation of peak distortion, peak shift and yield on the second column. Test compounds were selected on the basis of their physico-chemical properties (vapour pressure, acid-base properties, dipole moments, hydrogen bonding, complexation with metals, etc.). A number of differently pretreated capillaries were tested with these compounds under various external conditions. Accurate quantification and qualification of the activity of the capillary present difficulties. The test is a case of nearly ideal non-linear chromatography. When peaks of different sizes are superimposed, the tails lie on a common envelope. The k′ of the end of the tail is fixed, irrespective of the amount injected, and forms an important parameter in the evaluation. Reconstruction of the chromatogram with a k′ scale instead of a time scale eliminates the influence of carrier velocity and column length. The method is a sensitive tool for intermediate column testing and shows promises for surface characterization.     

Singlet exciplexes between a thioxanthone derivative and substituted aromatic quenchers: role of the resonance integral

Fluorescence quenching of a thioxanthone derivative by methyl- and methoxy-substituted benzenes (MeB and MeOB, respectively) is performed in solvents of different polarity. Emissive exciplexes are observed even in polar solvents and provide kinetic and spectroscopic data over a large scale of solvent polarity. These data were subsequently analyzed by use of a new theoretical model that leads to a thermodynamic relationship between exciplex and electron-transfer driving forces Delta G(exc) and Delta G(et), respectively. The remarkable agreement found between this model and both kinetic and spectroscopic data supports its validity. Moreover, the difference observed between MeB and MeOB compounds in quenching efficiency is analyzed by this model and provides the main parameters governing exciplex features, especially the resonance integral between locally excited and charge-transfer states.     

Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.

A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins.     

Line Intensities in the ν6Band of CH3F at 8.5 μm

Infrared absolute line intensities of the ν₆band of CH₃F have been measured around 8.5 μm using a diode-laser spectrometer. These line strengths were obtained by the equivalent width method and, for 13 lines, by fitting a Rautian profile to the measured shape of the lines. From these results, we have deduced the vibrational band strength to beS⁰_v= 9.66 ± 0.13 cm⁻²atm⁻¹at 296 K and the first Herman–Wallis factors.