Synthetic Communication: Synthesis of Optically Pure Analogues of D-Arginine Methyl Ester with Antiarrhythmic Activity

The synthesis of the methyl esters of optically pure trans and cis 4-guanidinocyclohexylglycine as rigid analogues of D-arginine methyl ester are described.     

Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp2?Csp and Csp3?Csp Bonds from Organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected “anti‐Michael” reactions observed for substituted sulfonylacetylenes.     

Organozinc Pivalate Reagents: Segregation,Solubility, Stabilization,and Structural Insights

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt‐supported organometallic reagents, because apart from their effectiveness in Negishi cross‐coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X‐ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p‐tolyl case system shows that in [D₈]THF solution these reagents exist as separated Me(p‐C₆H₄)ZnCl and Mg(OPiv)₂ species. Air exposure tests and X‐ray crystallographic studies indicate that Mg(OPiv)₂ enhances the air stability of aryl zinc species by sequestering H₂O contaminants. Coupling reactions of Me(p‐C₆H₄)ZnX (where X=different salts) with 4‐bromoanisole highlight the importance of the presence of Mg(OPiv)₂. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)₂Li₂(Cl)₂(OPiv)₂Zn].     

Large deflection of a non-linear,elastic, asymmetric Ludwick cantilever beam subjected to horizontal force,vertical force and bending torque at the free end

The investigated cantilever beam is characterized by a constant rectangular cross-section and is subjected to a concentrated constant vertical load, to a concentrated constant horizontal load and to a concentrated constant bending torque at the free end. The same beam is made by an elastic non-linear asymmetric Ludwick type material with different behavior in tension and compression. Namely the constitutive law of the proposed material is characterized by two different elastic moduli and two different strain exponential coefficients. The aim of this study is to describe the deformation of the beam neutral surface and particularly the horizontal and vertical displacements of the free end cross-section. The analysis of large deflection is based on the Euler–Bernoulli bending beam theory, for which cross-sections, after the deformation, remain plain and perpendicular to the neutral surface; furthermore their shape and area do not change. On the stress viewpoint, the shear stress effect and the axial force effect are considered negligible in comparison with the bending effect. The mechanical model deduced from the identified hypotheses includes two kind of non-linearity: the first due to the material and the latter due to large deformations. The mathematical problem associated with the mechanical model, i.e. to compute the bending deformations, consists in solving a non-linear algebraic system and a non-liner second order ordinary differential equation. Thus a numerical algorithm is developed and some examples of specific results are shown in this paper.     

Optimisation of sensor positions in random linear arrays based on statistical relations between geometry and performance

Due to the widespread use of acoustic arrays, optimisation techniques for array design, focused on improving array performance, have been widely published. This paper exploits the statistical relation between different measures of sidelobe levels and the spacing of elements in random linear arrays made up of a small number of sensors. This paper defines the methodology to obtain maximum probability functions, associating array geometry and performance. These maximum probability functions allow a pre-selection of those array geometries that are more likely to be associated to specified sidelobe level values. This pre-selection results in a significantly reduced computational burden.