Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

An Enumerative Geometry for Magic and Magilatin Labellings

A magic labelling of a set system is a labelling of its points by distinct positive integers so that every set of the system has the same sum, the magic sum. Examples are magic squares (the sets are the rows, columns, and diagonals) and semimagic squares (the same, but without the diagonals). A magilatin labelling is like a magic labelling but the values need be distinct only within each set. We show that the number of n × n magic or magilatin labellings is a quasipolynomial function of the magic sum, and also of an upper bound on the entries in the square. Our results differ from previous ones because we require that the entries in the square all be different from each other, and because we derive our results not by ad hoc reasoning but from a general theory of counting lattice points in rational inside-out polytopes. We also generalize from set systems to rational linear forms. Dedicated to the memory of Claudia Zaslavsky, 1917–2006 Received August 10, 2005     

Fabrication of material-independent morphology gradients for high-throughput applications

Gradient surfaces allow rapid, high-throughput investigations and systematic studies in many disparate fields, including biology, tribology and adhesion. We describe a novel method for the fabrication of material-independent morphology gradients, involving a two-step process of particle erosion followed by a chemical polishing procedure that preferentially removes features with a small radius of curvature as a function of time. Gradients are fabricated on aluminium surfaces, but they may be readily transferred to other materials via a replication technique, which allows for the production of identical roughness gradient samples with any chosen surface chemistry. The gradients have been characterized by means of scanning electron microscopy and optical profilometry. Standard roughness parameters (Ra, Rq, Rz, Sm and Sk) were calculated from optical profilometry data. The roughness has also been assessed over different wavelength windows by means of a fast Fourier transformation approach.     

Nonaqueous diazotization of 4-amino-3-arylisothiazole-5-carboxylate esters

4-Amino-3-arylisothiazole-5-carboxylate esters are converted to the corresponding desamino, chloro, bromo, and iodo esters by processes involving nonaqueous diazotization. These related procedures open up the possibility for the conversion of readily available heterocyclic ortho-amino esters and nitriles to related heterocyclic derivatives, which are not easily obtained by alternate routes.     

Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles

α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H₂ agonists of the arpromidine type.     

The neutral weak current of the nucleon

A brief review of the structure of the nucleon as determined through parity-violating electron scattering is presented. The relationship between the electromagnetic and neutral weak currents is developed in a pedagogical introduction. Recent results and present measurements are discussed.