New Chiral Ortho-P,S-Difunctionalized Aromatic Compounds

Abstract

A new method to prepare enantioenriched sulfinates was developed to obtain optically active ortho-methylsulfinyl(phenylphosphonates). It consists of a diastereoselective oxidation of sulfenates to sulfinates. Additionally, preliminary results concerning the synthesis of ortho-phophonylated benzylic thiol derivatives via a new P═S to P═C [1,4]-rearrangement and a first synthetic application of these compounds are also described.     

Stereoselective Cycloaddition of Monosubstituted Ketene to a Methyl Glyoxylate- and Threonine-Derived Imine: Synthesis of Optically Pure β-Lactamic α-Amino Ester with High Functionality

The reaction of chloroacetyl chloride and triethylamine with a chiral imine derived from the combination of methyl glyoxylate and protected L-threonine gave two optically active α-amino acid derivatives with a cis-substituted β-lactam skeleton in a 72:28 ratio. The major product is obtained in 59% yield by simple crystallisation.     

N-tert-Butoxycarbonyl (BOC) Deprotection Using Boron Trifluoride Etherate

A mild and efficient procedure is described for the removal of the tert-butoxycarbonyl (BOC) group using boron trifluoride etherate and molecular sieves in dichloromethane at room temperature. The scope of this procedure is explored for the deprotection of a variety of amines including amino acid derivatives.     

Alkoxyallene‐ynes: Selective Preparation of Bicyclo[5.3.0] Ring Systems Including a δ‐Alkoxy Cyclopentadienone

The development of an intramolecular rhodium(I)‐catalyzed Pauson–Khand reaction of alkoxyallene‐ynes with a proximal alkoxy group is reported. This reaction, in the presence of a [Rh(cycloocta‐1,5‐diene)Cl]₂/propane‐1,3‐diylbis(diphenylphosphane) system under a CO atmosphere, constitutes a powerful tool for selectively accessing carbo‐ and heterobicyclo[5.3.0] frameworks featuring an enol ether moiety. Through this procedure, a straightforward access to guaiane skeletons with a tertiary hydroxy group at the C10 position was achieved.     

1H MRS detection of glycine residue of reduced glutathione in vivo

Glutathione (GSH) is a powerful antioxidant found inside different kinds of cells, including those of the central nervous system. Detection of GSH in the human brain using ¹H MR spectroscopy is hindered by low concentration and spectral overlap with other metabolites. Previous MRS methods focused mainly on the detection of the cysteine residue (GSH-Cys) via editing schemes. This study focuses on the detection of the glycine residue (GSH-Gly), which is overlapped by glutamate and glutamine (Glx) under physiological pH and temperature. The first goal of the study was to obtain the spectral parameters for characterization of the GSH-Gly signal under physiological conditions. The second goal was to investigate a new method of separating GSH-Gly from Glx in vivo. The characterization of the signal was carried out by utilization of numerical simulations as well as experiments over a wide range of magnetic fields (4.0–14 T). The proposed separation scheme utilizes J-difference editing to quantify the Glx contribution to separate it from the GSH-Gly signal. The presented method retains 100% of the GSH-Gly signal. The overall increase in signal to noise ratio of the targeted resonance is calculated to yield a significant SNR improvement compared to previously used methods that target GSH-Cys residue. This allows shorter acquisition times for in vivo human clinical studies.     

Comparison of direct mass spectrometry methods for the on‐line analysis of volatile compounds in foods

For the on‐line monitoring of flavour compound release, atmospheric pressure chemical ionization (APCI) and proton transfer reaction (PTR) combined to mass spectrometry (MS) are the most often used ionization technologies. APCI‐MS was questioned for the quantification of volatiles in complex mixtures, but direct comparisons of APCI and PTR techniques applied on the same samples remain scarce. The aim of this work was to compare the potentialities of both techniques for the study of in vitro and in vivo flavour release. Aroma release from flavoured aqueous solutions (in vitro measurements in Teflon bags and glass vials) or flavoured candies (in vivo measurements on six panellists) was studied using APCI‐ and PTR‐MS. Very similar results were obtained with both techniques. Their sensitivities, expressed as limit of detection of 2,5‐dimethylpyrazine, were found equivalent at 12 ng/l air. Analyses of Teflon bag headspace revealed a poor repeatability and important ionization competitions with both APCI‐ and PTR‐MS, particularly between an ester and a secondary alcohol. These phenomena were attributed to dependency on moisture content, gas/liquid volume ratio, proton affinities and product ion distribution, together with inherent drawbacks of Teflon bags (adsorption, condensation of water and polar molecules). Concerning the analyses of vial headspace and in vivo analyses, similar results were obtained with both techniques, revealing no competition phenomena. This study highlighted the equivalent performances of APCI‐MS and PTR‐MS for in vitro and in vivo flavour release investigations and provided useful data on the problematic use of sample bags for headspace analyses. Copyright © 2013 John Wiley & Sons, Ltd.     

Convenient One‐Pot Procedures for the Synthesis of 2,2′:6′,2″‐Terpyridine

One‐pot reactions to produce 2,2′:6′,2″‐terpyridine (tpy) under mild conditions are described under both solventless and solvent‐assisted conditions. Tpy can be obtained in 32% yield in a simple one‐pot reaction, which can readily be scaled‐up to give large quantities of tpy. These new approaches are superior to those previously described because of the fast and efficient synthesis and purification of tpy.     

Synthesis of 3-methyl-7-[2-(dimethylaminoethyl)oximino]-5-arylcyclopenta [F] Benzoxazolinones,Potential Ligands of the 5HT1D Receptors

The synthesis of 3-methyl-7-[2-(dimethylaminoethyl)oximino]-5-arylcyclopenta [f] benzoxa-zolinones, potential ligands of the 5HT_1D receptors is described through a 4 steps reaction strategy from 3-methyl-6-acetyl benzoxazolinone.