Rational Development of Remote C−H Functionalization of Biphenyl: Experimental and Computational Studies

A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process.     

Coupling of a multilevel fast multipole method and a microlocal discretization for the 3-D integral equations of electromagnetism

The aim of this work is to propose an accurate and efficient numerical approximation for high frequency diffraction of electromagnetic waves. In the context of the boundary integral equations presented in F. Collino and B. Després, to be published in J. Comput. Appl. Math., the strategy we propose combines the microlocal discretization (T. Abboud et al., in: Third International Conference on Mathematical Aspects of Wave Propagation Phenomena, SIAM, 1995, pp. 178–187) and the multilevel fast multipole method (J.M. Song, W.C. Chew, Microw. Opt. Tech. Lett. 10 (1) (1995) 14–19). This leads to a numerical method with a reduced complexity, of order O(N^4/3ln(N)+N_iterN^2/3), instead of the complexity O(N_iterN²) for a classical numerical iterative solution of integral equations. Computations on an academic geometry show that the new method improves the efficiency, for a solution with a good level of accuracy. To cite this article: A. Bachelot et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Characterization of NOx species in dehydrated and hydrated Na- and Ba-Y, FAU zeolites formed in NO2 adsorption

Adsorbed ionic NO_x species formed upon the interaction of NO₂ with dehydrated or hydrated Na- and Ba-Y, FAU zeolites were characterized using FT-IR/TPD, solid state NMR, and XANES techniques. NO₂ disproportionates on both dehydrated catalyst materials forming NO⁺ and NO₃⁻ species. These ionic species are stabilized by their interactions with the negatively charged zeolite framework and the charge compensating cations (Na⁺ and Ba²⁺), respectively. Although the nature of the adsorbed NO_x species formed on the two catalysts is similar, their thermal stabilities are strongly dependent on the charge compensating cations. In the presence of water in the channels of these zeolite materials new paths open for reactions between NO⁺ and H₂O, and NO₂ and H₂O, resulting in significant changes in the adsorbed ionic species observed. These combined spectroscopic investigations afforded the understanding of the interactions between water and NO₂ on these zeolite catalysts.     

Contemplating Criteria for Science Education Reform: The Case of the Olympia School District

Proposals for current reform in science education elaborate national standards and a plethora of state-level interpretations commonly labeled as curriculum or learning frameworks. The purpose of this case study was to examine the dynamics of the science curriculum reform process in one of the first school districts to use the Georgia Framework for Learning Mathematics and Science as a basis for their reform initiative. The paper describes the ways in which members of the Olympia School District's Science Curriculum Committee participated in the science curriculum reform process, as well as their personal beliefs about the criteria needed for reform to take place. The results highlight the nature of metaphors guiding reform efforts; the influence of social, historical, economic, and political forces on the reform process; the use of local and professional languages as discourses for communicating about reform; and the complex power relations that influence the micropolitics of reform in the Olympia School District. This study has important implications for other teachers and school districts engaged in standards-based science curriculum reform. It points to the need for reform to include reflection and analysis of the role of teachers in the reform process and consideration of the purpose of science education reform in society.     

Density and uniqueness in percolation

Two results on site percolation on thed-dimensional lattice,d1 arbitrary, are presented. In the first theorem, we show that for stationary underlying probability measures, each infinite cluster has a well-defined density with probability one. The second theorem states that if in addition, the probability measure satisfies the finite energy condition of Newman and Schulman, then there can be at most one infinite cluster with probability one. The simple arguments extend to a broad class of finite-dimensional models, including bond percolation and regular lattices.     

Intramolecular dimers: a new design strategy for fluorescence-quenched probes

Fluorogenic probes dual-labeled with reporter and quencher dyes use a change in fluorescence to monitor biochemical events (e.g., substrate binding or enzyme digestion). Such events change the reporter-quencher distance, which affects fluorescence. Recently, it is has been shown that static quenching through intramolecular dimers is an important mechanism that can sometimes be more efficient than F?rster resonance energy transfer (FRET).     

A Mets motif peptide found in copper transport proteins selectively binds Cu(I) with methionine-only coordination

Mets motifs, which refer to methionine-rich sequences found in the high-affinity copper transporter Ctr1, also appear in other proteins involved in copper trafficking and homeostasis, including other Ctrs as well as Pco and Cop proteins isolated from copper-resistant bacteria. To understand the coordination chemistry utilized by these proteins, we studied the copper binding properties of a peptide labeled Mets7-PcoC with the sequence Met-Thr-Gly-Met-Lys-Gly-Met-Ser. By comparing this sequence to a series of mutants containing noncoordinating norleucine in place of methionine, we confirm that all three methionine residues are involved in a thioether-only binding site that is selective for Cu(I). Two independent methods, one based on mass spectrometry and one based on rate differences for the copper-catalyzed oxidation of ascorbic acid, provide an effective K(D) of approximately 2.5 microM at pH 4.5 for the 1:1 complex of Mets7-PcoC with Cu(I). These results establish that a relatively simple peptide containing an MX(2)MX(2)M motif is sufficient to bind Cu(I) with an affinity that corresponds well with its proposed biological function of extracellular copper acquisition.     

Suzuki-Miyaura cross-coupling of aryl and alkyl halides using palladium/imidazolium salt protocols

A simple new protocol for the high yielding Suzuki-Miyaura cross-couplings of aryl chlorides with aryl boronic acids using a palladium/imidazolium salt catalytic system is presented. The first examples of a palladium/imidazolium salt protocol for sp³-sp³ Suzuki-Miyaura couplings of alkyl halides are also disclosed.     

Quinazolines. VII. Synthesis of 1,3-Diamino-5,6-dihydrobenzo[f]quinazolines

Eighteen new 1,3-diamino-5,6-dihydrobenzo[f] quinazolines ( 6 , R. = alkyl, Cl, MeO) were synthesized via the condensation of appropriate 2-tetralones with cyanoguanidine under fusion conditions. Methods were developed for the preparation of a number of heretofore undescribed 2-tetralones as precursors. The final products can be viewed as conformationally rigid analogs of pyrimethamine ( 2 ), and are of interest as inhibitors of dihydrofolate reductase and as potential antimalarial and antitumor agents.     

Preparation of halo-F-methanes via potassium fluoride-halogen cleavage of halo-F-methylphosphonium salts

Treatment of halo-$\text{F}$-methylphosphonium salts with potassium fluoride and halogen (I₂, Br₂, ICl, IBr) gives modest yields of halo-$\text{F}$-methanes. This method of preparation augments the classical Hunsdiecker approach to these materials.