Synthesis of a New Diaazacrown Ether Compound Interconnected with an Azacrown Ether and Decorated with a Long Lipophilic Chain

The synthesis of an original compound consisting of an azacrown ether interconnected with a diazacrown ether bearing an alkyl chain is described herein. This derivative is promising for numerous applications.     

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1)

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively induced ethane elimination when M = Rh, whereas the related Ir systems prefer to decompose by alternative pathways.     

Iron‐Catalyzed Oxidative Heterocoupling Between Aliphatic and Aromatic Organozinc Reagents: A Novel Pathway for Functionalized Aryl–Alkyl Cross‐Coupling Reactions

Aryl–alkyl cross‐coupling products are obtained by the iron‐catalyzed oxidative heterocoupling of organozinc reagents under mild conditions. This novel reaction pathway is versatile, allowing for the use of primary and secondary aliphatic diorganozinc reagents as coupling partners as well as tolerating functionalized aryl‐ and alkylzinc reagents.

     

Asymmetric Magnesium‐Catalyzed Hydroboration by Metal‐Ligand Cooperative Catalysis

Asymmetric catalysis with readily available, cheap, and non‐toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first Mg^II‐catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal‐ligand cooperative catalysis pathway involving a non‐innocent ligand.     

Synthesis of an adenine N-3 substituted CBI adduct by alkylation of adenine with a 1-iodomethylindoline seco-CBI precursor

The synthesis of a 1,2,9,9a-tetrahydrocyclopropa[c]benz[e]indol-4-one (CBI)-adenine adduct via regioselective N-3 alkylation of adenine with a 1-(iodomethyl)-2,3-dihydro-1H-benzo[e]indol-5-ol (I-seco-CBI)-containing precursor is described. Spectroscopic analyses of the unlabeled and adenine-C8 carbon-13 labeled adducts utilizing ROESY NMR techniques allowed structural assignment of the alkylation product as the adenine N-3 substituted regioisomer. A stable-isotopically labeled version of the N-3 adduct incorporating six carbon-13 labels was also prepared by this method for use as an LC-MS internal standard. The cyclized CBI-containing compound was also found to alkylate adenine at elevated temperatures to produce the N-3 adduct albeit at a significantly slower rate than that observed for the I-seco-CBI precursor. Adenine alkylation with an I-seco-CBI precursor offers scalable and facile access to a CBI-adenine adduct facilitating its use as an efficacy marker for the development of duocarmycin-based ADCs.     

Biosynthesis‐Assisted Structural Elucidation of the Bartolosides,Chlorinated Aromatic Glycolipids from Cyanobacteria

The isolation of the bartolosides, unprecedented cyanobacterial glycolipids featuring aliphatic chains with chlorine substituents and C‐glycosyl moieties, is reported. Their chlorinated dialkylresorcinol (DAR) core presented a major structural‐elucidation challenge. To overcome this, we discovered the bartoloside (brt) biosynthetic gene cluster and linked it to the natural products through in vitro characterization of the DAR‐forming ketosynthase and aromatase. Bioinformatic analysis also revealed a novel potential halogenase. Knowledge of the bartoloside biosynthesis constrained the DAR core structure by defining key pathway intermediates, ultimately allowing us to determine the full structures of the bartolosides. This work illustrates the power of genomics to enable the use of biosynthetic information for structure elucidation.     

Conjugate heat transfer with Large Eddy Simulation for gas turbine components

CHT (Conjugate Heat Transfer) is a main design constraint for GT (gas turbines). Most existing CHT tools are developed for chained, steady phenomena. A fully parallel environment for CHT has been developed and applied to two configurations of interest for the design of GT. A reactive Large Eddy Simulations code and a solid conduction solver exchange data via a supervisor. A flame/wall interaction is used to assess the precision and the order of the coupled solutions. A film-cooled turbine vane is then studied. Thermal conduction in the blade implies lower wall temperature than adiabatic results and CHT reproduces the experimental cooling efficiency. To cite this article: F. Duchaine et al., C. R. Mecanique 337 (2009).     

Novel pharmaceutical applications of polysaccharides

The role of chemically characterized polysaccharides will be discussed in view of their immunostimulating activities. A possible correlation of fungal β-1.3/1.6-glucans differing in the branching pattern is demonstrated with in vivo tumor models. In a second part the possible role of sulfated polysaccharide structures as anticoagulating compounds is again correlated with polysaccharide structures and sulfate substitution pattern of these biopolymer derivatives.     

DNS of MHD turbulence in liquid metals based on the least dissipative modes

We investigate numerically the incompressible Navier-Stokes equations under an externally imposed magnetic field. The results obtained for the simplified geometry of a three dimensional periodic box and show a lower computational complexity and stronger relationship between the physical reality and its numerical representation. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)