Palladium-catalyzed reaction of boronic acids with chiral and racemic alpha-bromo sulfoxides

Palladium-catalyzed cross-coupling reactions of racemic alpha-bromo sulfoxides with boronic acids are carried out in either aqueous or nonaqueous medium with formation of a new C sp(3)-C sp(2) bond. The arylation of chiral alpha-bromo sulfoxides occurs without racemization. The cross-coupling reaction is general and gives high yields with arylboronic acids substituted with either donor or acceptor groups but gives poor results with heteroarylboronic acids. The best yields are obtained using degassed solvents and CsF instead of aqueous base. The use of aqueous base and the presence of oxygen favor the homocoupling side reaction.     

Olefin isomerisation versus hydrozirconation: a case of a stable beta-hydrogen-containing Zr-alkyl derivative

Details of the olefin isomerisation mechanism followed by monohydride constrained-geometry zirconium complexes have been clarified using the allyldimethylsilylcyclopentadienyl zirconium hydride model compound. DFT calculations on the model systems agree with the experimental results.     

An efficient and expeditious microwave‐assisted synthesis of quinoxaline derivatives via nucleophilic heteroaromatic substitution

A series of 2‐substituted quinoxaline derivatives including five novel compounds have been successfully synthesized from 2‐chloroquinoxaline using microwave methodology. The yields of the quinoxalines synthesized through this method, were an improvement over the thermal methods usually employed.     

Organotitanoxanes with unique structure among transition-element organometallic oxide derivatives

The synthesis of novel titanoxane compounds, [{(TiCl)(Ti)[mu-(eta(5)-C5Me4SiMe2O-kappaO)]2(mu-O)}2(mu-O)] (4) and [{Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)](mu-O)}6] (5), by controlled hydrolysis of a dinuclear titanium/oxo complex is described. Complexes 4 and 5 show unprecedented structural features for organometallic oxide derivatives of transition elements and represent unique fully characterized examples of tetra- and hexanuclear organo-transition-metal oxide compounds with an open-chain and a monocyclic structure, respectively.     

Exploring benzylic gem-C(sp3)–boron–silicon and boron–tin centers as a synthetic platform

A stepwise build-up of multi-substituted C_sp³ carbon centers is an attractive, conceptually simple, but often synthetically challenging type of disconnection. To this end, this report describes how gem-α,α-dimetalloid-substituted benzylic reagents bearing boron/silicon or boron/tin substituent sets are an excellent stepping stone towards diverse substitution patterns. These gem-dimetalloids were readily accessed, either by known carbenoid insertion into C–B bonds or by the newly developed scalable deprotonation/metallation approach. Highly chemoselective transformations of either the C–Si (or C–Sn) or the C–B bonds in the newly formed gem-C_sp³ centers have been achieved through a set of approaches, with a particular focus on exploiting the synthetically versatile polarity reversal in organometalloids by λ³-aryliodanes. Of particular note is the metal-free arylation of the C–Si (or C–Sn) bonds in such gem-dimetalloids via the iodane-guided C–H coupling approach. DFT calculations show that this transfer of the (α-Bpin)benzyl group proceeds via unusual [5,5]-sigmatropic rearrangement and is driven by the high-energy iodine(iii) center. As a complementary tool, the gem-dimetalloid C–B bond is shown to undergo a potent and chemoselective Suzuki–Miyaura arylation with diverse Ar–Cl, thanks to the development of the reactive gem-α,α-silyl/BF₃K building blocks.

This work explores divergent reactivity of the benzylic gem-boron–silicon and boron–tin double nucleophiles, including the arylation of the C–B bond with Ar–Cl, along with a complementary oxidative λ³-iodane-guided arylation of the C–Si/Sn moiety.     

Damping of structural vibrations in beams and elliptical plates using the acoustic black hole effect

Flexural waves in beams and plates slow down if their thickness decreases. Such property was used in the past for establishing the theory of acoustic black holes (ABH). The aim of the present paper is to establish reliable numerical and experimental approaches for designing, modelling and manufacturing an effective passive vibration damper using the ABH effect. The effectiveness of such vibration absorbers increases with frequency. Initially, the dynamic behaviour of an Euler-Bernoulli beam is expressed using the Impedance Method, which in turn leads to a Riccati equation for the beam impedance. This equation is numerically integrated using an adaptive Runge-Kutta-Fehlberg method, yielding the frequency- and spatially-dependent impedance matrix of the beam, from which the reflection matrix is obtained. Moreover, the mathematical model can be extended to incorporate an absorbing film that assists for reducing reflected waves from the truncated edge. Therefore, the influence of the geometrical and material characteristics of the absorbing film is then studied and an optimal configuration of these parameters is proposed. An experiment consisting of an elliptical plate with a pit of power-law profile placed in one of its foci is presented. The elliptical shape of the plate induces a complete focalisation of the waves towards ABH in case they are generated in the other focus. Consequently, the derived 1-D method for an Euler-Bernoulli beam can be used as a phenomenological model assisting for better understanding the complex processes in 2-D elliptical structure. Finally, both, numerical simulations and experimental measurements show significant reduction of vibration levels.     

Tangential Homology for Defect Detection in the Time of Flight Diffraction Method (TOFD)

Ultrasonic non-destructive testing (NDT) techniques are widely used in industry to evaluate properties of a component, material or system without causing any damage. The time of flight diffraction method (TOFD) is regarded as a valuable procedure for the detection of welding defects. We propose an innovative concept for NDT relying on tangential homology. The novel technique allows us to analyze topological properties of manifolds from discrete data. This in turn provides an automated classification of TOFD defects which does not require any interactions with a human operator. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lewis acid fragmentation of a lithium aryloxide cage: generation of new heterometallic aluminium-lithium species

Heterometallic aluminium-lithium species were prepared by the fragmentation reaction of the hexametallic cage compound [Li{2,6-(MeO)(2)C(6)H(3)O}](6) (1) with alkyl aluminium derivatives. Depending on the aluminium precursor, the species formed present different nuclearities in the solid state as shown by single crystal X-ray analysis. Spectroscopic and computational studies have been performed to study the nuclearity of the synthesized compounds in solution.     

Kinetic and mechanism of the homogeneous,unimolecular elimination of α,β‐unsaturated aldehydes in the gas phase

The gas phase thermal decarbonylation of α,β‐unsaturated aldehydes E‐2‐butenal and E‐3‐phenyl‐2‐methylpropenal was studied in a static system over the temperature range 380.5–490.0 °C and pressure range 55.5–150 Torr. The reactions are homogeneous and unimolecular and obey a first‐order rate law. The rate coefficient is represented by the following Arrhenius equations: The elimination products of 2‐butenal are propene and CO gas, while 3‐phenyl‐2‐methylpropenal produces α‐methylstyrene, cis‐trans‐β‐methylstyrene, indan, and CO gas. Kinetic and thermodynamic parameters suggest these elimination reactions to proceed through a three‐membered cyclic transition state type of mechanisms. However, a two steps mechanisms for the formation of a carbene type of intermediate through a four‐membered cyclic transition structure can not be overlooked. Copyright © 2007 John Wiley & Sons, Ltd.