Asymmetric Diels-Alder, Michael, and aldol reactions using a planar chiral 1,3-oxazol-2(3H)-one derived from (R)-(+)-4-hydroxy-[2.2]paracyclophane

(+)-(R)-[2.2]Paracyclophane[4,5-d]-1,3-oxazol-2(3H)-one exhibiting planar chirality has been used as a chiral auxiliary in asymmetric Diels-Alder, Michael, and aldol reactions of alpha,beta-unsaturated carboxy and enolate imides, respectively. The endo-exo- and face-diastereoselectivity is good and is controlled by the spatial relationship between the prochiral center and the C9-C10 ethylene bridge of the [2.2]paracyclophane moiety. The chiral auxiliary is easily removed and quantitatively recovered.     

Nucleus- and side-chain fluorinated 3-substituted indoles by a suitable combination of organometallic and radical chemistry

Regioselectively fluoro-, trifluoromethyl- and trifluoromethoxy-substituted 3-methyleneindolines have been prepared using a four-step procedure involving metalation/bromination of fluorinated Boc-protected anilines, N-propargylation of the resulting o-bromoarylcarbamate and reductive radical cyclization of the product with tributyltin hydride/AIBN. 3-Methyleneindolines, as valuable, versatile intermediates, can be transformed into highly functionalized 3-substituted indoles by ene-type reactions using different enophiles. Thus, fluoro-, trifluoromethyl- and trifluoromethoxy-substituted diethyl 2-hydroxy-2-[(1H-indol-3-yl)methyl]malonates, ethyl 2-hydroxy-3-(1H-indol-3-yl)propionates and ethyl 2-hydroxy-3-(1H-indol-3-yl)-2-trifluormethylpropionates were obtained in 77-86% yield by simply heating the corresponding tert-butyl 3-methyleneindoline-1-carboxylate with an equimolar amount of diethyl ketomalonate, ethyl glyoxalate and ethyl 3,3,3-trifluoropyruvate, respectively, at 100 °C, without solvent, for 0.5-4 h.     

Synthesis of Sulfoxides by Phase Transfer Catalyzed Oxidation of Sulfides by Cerium(IV) Ammonium Nitrate

Diaryl, dialkyl and alkyl aryl sulfides are oxidized by cerium (IV) ammonium nitrate in H₂ O/CH ₂ Cl ₂, in the presence of tetra-n-butylammonium bromide, at room temperature, to give sulfoxides in yields ranging between 90 and 100%.     

A multi-sensing scheme based on nonlinear coupled micromachined resonators

A new multi-sensing scheme via nonlinear weakly coupled resonators is introduced in this paper, which can simultaneously detect two different physical stimuli by monitoring the dynamic response around the first two lowest modes. The system consists of a mechanically coupled bridge resonator and cantilever resonator. The eigenvalue problem is solved to identify the right geometry for the resonators to optimize their resonance frequencies based on mode localization in order to provide outstanding sensitivity. A nonlinear equivalent model is developed using the Euler–Bernoulli beam theory while accounting for the geometric and electrostatic nonlinearities. The sensor's dynamics are explored using a reduced-order model based on two-mode Galerkin discretization, which reveals the richness of the response. To demonstrate the proposed sensing scheme, the dynamic response of the weakly coupled resonator is investigated by tuning the stiffness and mass of the bridge and cantilever resonators, respectively. With its simple and scalable design, the proposed system shows great potential for intelligent multi-sensing detection in many applications.

     

First general approach to cyclohex-3-ene-1,1-bis(phosphonates) by Diels-Alder cycloaddition of tetraethyl vinylidenebis(phosphonate) to 1,3-dienes

Tetraethyl vinylidenebis(phosphonate) (VBP) reacts smoothly with substituted 1,3-dienes at 90-110 degrees C without solvent to give the corresponding cyclohex-3-ene-1,1-bis(phosphonates) in good yields (60-85%). With nonsymmetrically substituted dienes, mixtures of regioisomers are obtained, the regioisomeric ratio being exclusively controlled by electronic effects. Danishefsky's diene allows tetraethyl 4-oxocyclohex-2-ene-1,1-bis(phosphonate) to be obtained in an 81% overall yield after the acid-catalyzed hydrolysis of the Diels-Alder cycloadduct. With 2,3-dimethoxy-1,3-butadiene, a mixture of regioisomeric dimethoxycyclohexene-1,1-bis(phosphonates) is formed by the VBP-catalyzed isomerization of the normal Diels-Alder cycloadduct. The mixture converges into tetraethyl 3,4-dimethoxycyclohex-2-ene-1,1-bis(phosphonate) at prolonged reaction times.     

Internal resonance in the higher-order modes of a MEMS beam: experiments and global analysis

This work investigates the dynamics of a microbeam-based MEMS device in the neighborhood of a 2:1 internal resonance between the third and fifth vibration modes. The saturation of the third mode and the concurrent activation of the fifth are observed. The main features are analyzed extensively, both experimentally and theoretically. We experimentally observe that the complexity induced by the 2:1 internal resonance covers a wide driving frequency range. Constantly comparing with the experimental data, the response is examined from a global perspective, by analyzing the attractor-basins scenario. This analysis is conducted both in the third-mode and in fifth-mode planes. We show several metamorphoses occurring as proceeding from the principal resonance to the 2:1 internal resonance, up to the final disappearance of the resonant and non-resonant attractors. The shape and wideness of all the basins are examined. Although they are progressively eroded, an appreciable region is detected where the compact cores of the attractors involved in the 2:1 internal resonance remain substantial, which allows effectively operating them under realistic conditions. The dynamical integrity of each resonant branch is discussed, especially as approaching the bifurcation points where the system becomes more vulnerable to the dynamic pull-in instability.

     

Rotational barriers of biphenyls having heavy heteroatoms as ortho-substituents: experimental and theoretical determination of steric effects

The free energies of activation for the aryl-aryl rotation of 17 biphenyl derivatives, bearing a heavy heteroatom (S, Se, Te, P, Si, Sn) as ortho substituent, have been measured by variable temperature NMR. These numbers, so called B values, represent a meaningful measure of the steric hindrance exerted by the selected substituents. DFT computations match quite satisfactorily the experimental barriers and the ground state geometries as well (determined, in two cases, by X-ray diffraction). The present values extend the available list of B values and thus provide an enlarged basis for the compilation of the space requirements of standard substituents, based solely on experimental determinations.