Using E-Exercise Bases in Mathematics: Case Studies at University

E-Exercise Bases (EEB) are now used in the teaching of mathematics, especially at university. We discuss here the consequences of their use on the students’ activity during computer lab sessions. Results stem from observations of several teaching designs organised in different French universities with three e-exercise bases. The analysis focuses on new tasks and on specific solving strategies, which appear using these resources. Moreover, specific didactic contract clauses are studied.     

Site‐ and Enantioselective C−H Oxygenation Catalyzed by a Chiral Manganese Porphyrin Complex with a Remote Binding Site

A chiral manganese porphyrin complex with a two‐point hydrogen‐bonding site was prepared and probed in catalytic C?H oxygenation reactions of 3,4‐dihydroquinolones. The desired oxygenation occurred with perfect site selectivity at the C4 methylene group and with high enantioselectivity in favor of the respective 4S‐configured secondary alcohols (12 examples, 29–97 % conversion, 19–68 % yield, 87–99 % ee). Mechanistic studies support the hypothesis that the reaction proceeds through a rate‐ and selectivity‐determining attack of the reactive manganese oxo complex at the hydrogen‐bound substrate and an oxygen transfer by a rebound mechanism.     

First experimental evidence of potassium ordering in layered k4co7o14

The layered P2-K4Co7O14 oxide has been prepared and characterized by means of X-ray diffraction, electrical conductivity, thermopower, and magnetic measurements. The crystal structure of K4Co7O14 (P6(3)/m space group, Z=2, a=7.5171(1) A, and c=12.371(1) A) consists of a stacking of slabs of edge-shared CoO6 octahedra with K+ ions occupying ordered positions in the interslab space, leading to a a0 radical7xa0 radical7 supercell. Potential energy calculations at 0 K are in good agreement with the ordered distribution of potassium ions in the (ab) plane. This oxide is metallic, and the magnetic susceptibility is of Pauli-type, which contrasts with the Curie-Weiss behavior of the homologous NaxCoO2 (x approximately 0.6) oxide with close alkali content. The thermopower at room temperature is about one-third that of polycrystalline Na0.6CoO2.     

Rapid Synthesis of New 5‐Nitroimidazoles as Potential Antibacterial Drugs via VNS Procedure

Original 4‐arylsulfonylmethyl‐5‐nitroimidazoles were prepared by reacting four chloromethylaryl sulfones with 5‐nitroimidazole derivatives via a vicarious nucleophilic substitution (VNS) of hydrogen reaction.     

Weinreb Amide,Ketone and Amine as Potential and Competitive Secondary Molecular Stations for Dibenzo-[24]Crown-8 in [2]Rotaxane Molecular Shuttles

This paper reports the synthesis and study of new pH-sensitive DB24C8-based [2]rotaxane molecular shuttles that contain within their axle four potential sites of interaction for the DB24C8: ammonium, amine, Weinreb amide, and ketone. In the protonated state, the DB24C8 lay around the best ammonium site. After either deprotonation or deprotonation-then-carbamoylation of the ammonium, different localizations of the DB24C8 were seen, depending on both the number and nature of the secondary stations and steric restriction. Unexpectedly, the results indicated that the Weinreb amide was not a proper secondary molecular station for the DB24C8. Nevertheless, through its methoxy side chain, it slowed down the shuttling of the macrocycle along the threaded axle, thereby partitioning the [2]rotaxane into two translational isomers on the NMR timescale. The ketone was successfully used as a secondary molecular station, and its weak affinity for the DB24C8 was similar to that of a secondary amine.     

Spotlight on Photoinduced Aryl Migration Reactions

Rearrangement reactions are certainly one of the most useful approaches towards complex structures in organic chemistry. With efficient conditions, it is indeed possible to convert simple substrates into highly functionalized products. Moreover, combining this approach with an attractive initiation process, such as visible-light catalysis, makes these reactions particularly powerful. Recently, tremendous improvements have been made, owing to a better understanding of photoredox mechanisms. In this review, recent progress on visible-light aryl migration reactions is discussed, focusing especially on Smiles rearrangement and related reactions.     

Impact of Heteroatom Substitution on Dual-State Emissive Rigidified 2-(2’-hydroxyphenyl)benzazole Dyes: Towards Ultra-Bright ESIPT Fluorophores**

2-(2’-Hydroxyphenyl)benzazole (HBX) fluorophores are well-known excited-state intramolecular proton transfer (ESIPT) emitters largely studied for their synthetic versatility, photostability, strong solid-state fluorescence and ability to engineer dual emission, thus paving the way to applications as white emitters, ratiometric sensors, and cryptographic dyes. However, they are heavily quenched in solution, due to efficient non-radiative pathways taking place as a consequence of the proton transfer in the excited-state. In this contribution, the nature of the heteroring constitutive of these rigidified HBX dyes was modified and we demonstrate that this simple structural modification triggers major optical changes in terms of emission color, dual emission engineering, and importantly, fluorescent quantum yield. Investigation of the photophysical properties in solution and in the solid state of a series of ethynyl-TIPS extended HBX fluorophores, along with ab initio calculations demonstrate the very promising abilities of these dyes to act as bright dual-state emitters, in both solution (even in protic environments) and solid state.     

Search for a Strong,Virtually “No‐Shift” Hydrogen Bond: A Cage Molecule with an Exceptional OH⋅⋅⋅F Interaction

Reported herein is the synthesis of a molecule containing an unusually strong hydrogen bond between an OH donor and a covalent F acceptor, a heretofore somewhat ill‐defined if not controversial interaction. This unique hydrogen bond is to a large extent a product of the tight framework of the rigid caged system. Remarkably, the interaction shows little to no perceptible shift in the OH stretch of the IR spectrum relative to appropriate nonhydrogen‐bound standards in fairly non‐interactive solvents. This fascinating example of what has been termed a virtual “no‐shift” hydrogen bond is investigated through NMR (coupling constants, isotopic chemical shift perturbations, proton exchange rates) and IR studies which all tell a consistent story.