Transition-Metal-Free α-Arylation of β-Keto Amides via an Interrupted Insertion Reaction of Arynes

Direct α-arylation reactions of secondary β-keto amides with arynes, generated by fluoride-induced elimination of ortho-silyl aryltriflates, are described. The transformation proceeds via an interrupted insertion reaction of arynes and leads to densely functionalized aromatic compounds exhibiting a chiral 'all carbon' quaternary center under transition-metal-free conditions. An organocatalytic asymmetric version of the reaction also proved possible, affording the proof of concept that arynes can be involved in enantioselective transformations.     

Design of an inversion center between two helical segments

A new strategy is proposed to control the relative orientation of two folded helical oligomers in such a way that they diverge from an aromatic linker and have opposite helical handedness. Mutual steric exclusion between the two helices results from the fact that they cannot be at the same time folded and on the same side of the linker. The concept is validated using the helical conformations of oligoamides of 8-amino-2-quinolinecarboxylic acid, but it should be applicable to many families of oligomers and leads to the first designed meso-helices.     

Chemistry of the 2-deoxyribonolactone lesion in oligonucleotides: cleavage kinetics and products analysis

Deoxyribonolactone in DNA is an oxidized abasic site damage that is produced by a variety of physical and chemical agents such as gamma-irradiation and ene-diyne antibiotics. The extent and biological significance of the lesion are poorly documented due to the high lability of the damaged DNA. The chemistry of degradation of deoxyribonolactone-containing DNA was investigated using oligonucleotides of different length (5-, 11-, 23-, 34-mers) in which the lactone was photochemically generated, as already reported, from oligonucleotide precursors containing a photoactive nitroindole residue. The procedure was successfully extended to double-strand synthesis by irradiation of the preformed duplex in which one strand contained the nitroindole residue. The degradation kinetics were investigated as a function of pH, temperature, length, and ionic strength. The cleavage fragments resulting from beta- and delta-eliminations were isolated and identified by (1)H NMR. It was found that the lesion is extremely sensitive to pH and temperature while slightly dependent upon ionic strength, length, and sequence. The cleavage rates for the beta- and delta-elimination steps are of the same order of magnitude. The deoxyribonolactone site leads to greater instability of DNA than the "regular" deoxyribose abasic site.     

Improved enantioselective synthesis of natural striatenic acid and its methyl ester

This letter describes the improved and efficient enantioselective synthesis of natural striatenic acid, isolated from Cheilolejeunea serpentina, and its methyl ester starting from a readily available enantiopure building block.     

Bis-phosphonates-ultra small superparamagnetic iron oxide nanoparticles: a platform towards diagnosis and therapy

A new type of multifunctional magnetic nano-platform for diagnosis and therapy applications was designed using bisphosphonate/carboxylic ligands.     

Glycomimetics and glycodendrimers as high affinity microbial anti-adhesins

Adhesion to epithelial surface is often the first step in bacterial and viral infection. In this process, the microbes use a variety of proteins for interaction with host carbohydrates presented as glycoconjugates on cell surfaces. Crystal structures of adhesin and lectin binding sites in complexes with oligosaccharide open the route for design and synthesis of glycomimetics, glycodendrimers, and glycopolymers that are able to block infection at an early stage.     

Injection coupling with high amplitude transverse modes: Experimentation and simulation

High frequency combustion instabilities have technical importance in the design of liquid rocket engines. These phenomena involve a strong coupling between transverse acoustic modes and combustion. They are currently being investigated by combining experimentation and numerical simulations. On the experimental level, the coupling is examined in a model scale system featuring a multiple injector combustor (MIC) comprising five coaxial injectors fed with liquid oxygen and gaseous methane. This system is equipped with a novel VHAM actuator (Very High Amplitude Modulator) which comprises two nozzles and a rotating toothed wheel blocking the nozzles in an alternate fashion. This device was designed to obtain the highest possible levels of transverse oscillation in the MIC. After a brief review of the VHAM, this article reports cold flow experiments using this modulator. Velocity maps obtained under resonant conditions using the VHAM are examined at different instants during a cycle of oscillation. Experimental data are compared with numerical pressure and velocity fields obtained from an acoustic solver. The good agreement observed in the nozzle vicinity indicates that numerical simulations can be used to analyze the complex flow field generated by the VHAM. To cite this article: Y. Mery et al., C. R. Mecanique 337 (2009).     

Catalyst- and halogen-free regioselective Friedel-Crafts α-ketoacylations

Fast, efficient and green! Highly regioselective and efficient catalyst- and halogen-free Friedel-Crafts α-ketoacylation reactions leading to heterocycles functionalized with a very versatile 1,3-diketone moiety are described. The reactions rely on microwave-assisted domino Wolff rearrangement/Friedel-Crafts sequences from 2-diazo-1,3-diketones via transient, highly reactive α-keto ketene intermediates.