The synthesis of DL-1-(hexadecanoyloxy)methyl- and 1-O-hexadecanoyl-inositols as potential inhibitors of phospholipase C

The synthesis of racemic analogues of phosphatidylinositol (PI) and phosphatidylinositol 4,5-bisphosphate (PIP₂) starting from myo-inositol is described. Inositol derivatives with and without homologalion at C(l) and with and without ionic groups (phosphate or sulfate) at C(4) and C(5) were prepared as well as homologated derivatives with deoxy composition at C(2) and/or C(6). In all these compounds, palmitate ester groups were introduced in place of the diacylglyceryl group of PI or PIP₂.     

Contribution à l'étude du comportement de la catéchine en milieu alcalin

Contribution to the study of the behaviour of catechin in alkaline medium When catechin ( 1 ) is warmed with aqueous alkali it first undergoes rapid epimerisation. After some time a novel bridged carbocyclic enol, catechinic acid ( 3 ) separates out and may be isolated in excellent yield. Eventually catechinic acid isomerises to 2-(3′,4′-dihydroxyphenyl)-3,9-epoxy-6-oxo-bicyclo[3,3,1]-non-7-en-8,9-diol ( 4 ) via an open chain anion ( 5 ) which is also involved in the epimerisation of catechin. Assignments of structure are given and the equilibria observed are discussed.     

Rapid and diverse route to natural product-like biaryl ether containing macrocycles

A two-step sequence involving an Ugi four-component reaction and an intramolecular nucleophilic aromatic substitution (S_NAr) has been developed for the rapid access to biaryl-ether containing macrocycles. In the course of this study, we documented that ammonium chloride can promote the Ugi-4CR in non-polar aprotic solvent (toluene) without the interference of an alternative Passerini reaction. Solid phase synthesis of macrocycles by this two-step sequence was also developed using polymer (Wang resin) supported α-(4′-fluoro-3′-nitro)phenethyl isocyanoacetate as one of the inputs.     

Copper reagents: a new and efficient solution for the selective addition of metallated propargylic amines to aldehydes

[reaction: see text] Anti alpha-amino-homopropargylic alcohols are prepared by addition of metallated propargylic amines to aldehydes. Among the four organometallic (LI, Zn, Ti, Cu) derivatives used, the most effective are the copper reagents.     

High-pressure structure of Li2CO3

The high-pressure behavior of Li₂CO₃ is studied up to 25 GPa with synchrotron angle-dispersive powder X-ray diffraction in diamond anvil cells and synthesis using a multi-anvil apparatus. A new non-quenchable hexagonal polymorph (P6₃/mcm, Z=2) occurs above 10 GPa with carbonate groups in a staggered configuration along the c-axis—a=4.4568(2) Å and c=5.1254(6) Å at 10 GPa. Two columns of face-shared distorted octahedra around the Li atoms are linked through octahedral edges. The oxygen atoms are coordinated to one carbon atom and four lithium atoms to form a distorted square pyramid. Splittings of X-ray reflections for the new polymorph observed above about 22 GPa under non-hydrostatic conditions arise from orthorhombic or monoclinic distortions of the hexagonal lattice. The results of this study are discussed in relation to the structural features found in other Me₂CO₃ carbonates (Me: Na, K, Rb, Cs) at atmospheric conditions.     

Detection of banned meat and bone meal in feedstuffs by near-infrared microscopic analysis of the dense sediment fraction

In this paper we present an alternative method for detection of meat and bone meal (MBM) in feedstuffs by near-infrared microscopic (NIRM) analysis of the particles in the sediment fraction (dense fraction (d >1.62) from dichloroethylene) of compound feeds. To apply this method the particles of the sediment fraction are spread on a sample holder and presented to the NIR microscope. By using the pointer of the microscope the infrared beam is focussed on each particle and the NIR spectrum (1112–2500 nm) is collected. This method can be used to detect the presence of MBM at concentrations as low as 0.05% mass fraction. When results from the NIRM method were compared with the classical microscopic method, a coefficient of determination (R²) of 0.87 was obtained. The results of this study demonstrated that this method could be proposed as a complementary tool for the detection of banned MBM in feedstuffs by reinforcement of the monitoring of feeds.     

Le diptérocarpol—II Stéréochimie en C-13 et en C-17

Various reactions of ring D of dipterocarpol (hydroxy-dammarenone-II) show this triterpene to have the configuration 13β, 17H, in accordance with biogenetic speculations.     

Regioselective palladium-catalyzed phenylation of ethyl 4-oxazolecarboxylate

The efficient and regioselective palladium-catalyzed C-2 arylation of ethyl 4-oxazolecarboxylate 1 with phenyliodide is described. The different parameters (solvent, base, ligand and catalyst) for the optimal conditions of this arylation process have been screened.     

Synthesis of new vitamin D3 analogues with a decalin-type CD-ring

Vitamin D analogues, characterized by a decalin CD-ring fragment are described.