Synthesis of chiral 2′,3′-pyranone(pyrrolidinone)-fused tryptamines

Chiral pyrano- and pyrrolidino-fused tryptamines were prepared by a diasteroselective trimolecular condensation between indole, Garner's aldehyde and Meldrum's acid, followed by selective functional group transformations.     

RSOS Models and Jantzen–Seitz Representations of Hecke Algebras at Roots of Unity

A special family of partitions occurs in two apparently unrelated contexts: the evaluation of one-dimensional configuration sums of certain RSOS models, and the modular representation theory of symmetric groups or their Hecke algebras H_m. We provide an explanation of this coincidence by showing how the irreducible H_m-modules which remain irreducible under restriction to H_{m_1} (Jantzen–Seitz modules) can be determined from the decomposition of a tensor product of representations sl_n.     

Ferrocenyltrithiocarbonates : I. Direct access from α-ferrocenylcarbinols by a SNi mechanism. Absolute x-ray structure determination of (R)-ferrocenylmethylmethane S-methyl-trithiocarbonate

¹⁰³Rh Chemical shifts of a variety of mono- and di-nuclear rhodium carbonyl complexes are reported together with the modifications to the probe and decoupler unit of a JEOL PS-100 PFT spectrometer which enable these ¹⁰³Rh-decoupled ¹³C NMR measurements to be made. These data are discussed in conjunction with ¹³C NMR data on other rhodium carbonyls.     

The syntheses of 16a'-homo-leurosidine and 16a'-homo-vinblastine. Generation of atropisomers

The synthesis of 16a'-homo-leurosidine was achieved through enantioselective generation of a ring D'-seco-precursor 33 (without requirement of a chiral auxiliary). Its cyclization provided the N(b')-quaternary salt 35 with a configuration corresponding to the atropisomeric form 8a rather than 8b of the target product. On debenzylation, the amine 8a was obtained and found not to isomerize thermally to the anticipated atropisomer 8b (in contrast to its lower homologue, with its formation of natural leurosidine). However, on protonation, a 1:1 mixture of atropisomers of 16a'-homo-leurosidine was obtained. A synthesis of 16a'-homo-vinblastine provided two atropisomers 5a and 5b for the free base at equilibrium (1:2.3 at room temperature in CDCl(3)), with a shift to the major conformer 5b with increasing solvent acidity or decreasing temperature. The synthesis was achieved through a stereoselective inversion of the tertiary hydroxyl function in the enantioselectively generated C-20' progenitor 39.     

Structural insights into aluminum chlorofluoride (ACF)

The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction.     

Dipolar and V-shaped structures incorporating methylenepyran and diazine fragments

Thirteen novel dipolar and V-shaped chromophores with pyranylidene electron-donating part, diazine electron-withdrawing part and various π-linkers were synthesized. The extent of intramolecular charge transfer, structure-property relationships and optical properties were further investigated by UV/Vis absorption, electrochemistry, and DFT calculations.     

Practical Syntheses of Functionalized 1-Oxo-L,2,3,4-Tetrahydro-β-carboline-3-carboxylic Acid Esters

Three methods have been proposed for the preparation of functionalized 1-oxo-1,2,3,4-tetrahydro-β-carboline-3 carboxylates (3) from which the “acylazide formation-Curtius rearrangement-acid catalyzed ring closure” sequence starling from hemi-ester hemi-acids (8) seemed to be quite general.     

Quaterthiophene-based dimers containing an ethylene bridge: molecular design,synthesis, and optoelectronic properties

Two quaterthiophene-based dimers including an ethylene bridge have been designed and efficiently prepared; experimental and computational studies show a promising potential as semiconducting material with a charge transport of higher dimensionality compared to quaterthiophene.     

Fluorinated organic chemicals: Prospects in New Electrochemical Energy Technologies

This contribution has been partly adapted from a special lecture intended to commemorate the Nobel prize, awarded one century ago, to Henri Moissan. It, is focused on fluorinated and perfluorinated molecules and macromolecules used in electrochemical energy sources, i.e. storage and conversion of energy. The latter, which figure indisputably among New Energy Technologies, include lithium batteries and fuel cells based on polymeric membranes both of which have tremendous development potential in terms of performances, safety and cost reductions. The advantages inherent in fluorine, in particular its electron-withdrawing effect and the oxidation stability that it provides to the carbon-fluorine bond, make it an asset in the search for new organic molecular and macromolecular anions with extensive delocalization of the negative charge, usable both in lithium batteries and fuel cells. As for fluorinated and perfluorinated macromolecule backbones, they are currently the reference material in fuel cell ionomeric membranes but some of them are also good candidates for use in lithium-ion batteries. This paper, far from being exhaustive, also emphasizes the economic aspects that influence material selection and also govern the future of basic research.