Thermal reactions of tributyltin hydride with alpha-azido esters: unexpected intervention of tin triazene adducts under both nonradical and radical conditions

Thermal reaction of various alpha-azido esters with Bu(3)SnH in refluxing benzene results in smooth production of 3-(tributylstannyl)-1-triazene adducts affording cyclized 1,2,3-triazol-4-ones in preference to reduced amines and thence provides a new useful method for the preparation of these triazole derivatives. In the presence of AIBN the occurrence of triazene products still remains important or even exclusive and, consequently, generation of the expected stannylaminyl radicals is seriously limited. With 2-azidomalonates and alpha-azido-beta-keto esters stannyltriazenes can similarly occur in the absence of the radical initiator, but in the latter cases the ensuing triazenes undergo preferential cyclization onto the ketone moiety to give reactive hydroxytriazolines. Contrary to alpha-azido esters, in the presence of AIBN alpha-azido-beta-keto esters as well as azidomalonates give rise only to the usual stannylaminyl radicals. A possible explanation for the different behavior of the mono- and dicarbonyl azides in the presence of AIBN is put forward.     

Intramolecular cyclization of acyl radicals onto the azido group: a new radical approach to cyclized lactams

[reaction: see text] Aryl- and alkyl-derived azidoacyl radicals, generated from thiolesters by intramolecular homolytic substitution at the sulfur, can undergo five- and six-membered cyclization onto the azido moiety to give cyclized lactams.     

alpha-(Arylthio)imidoyl Radicals: [3 + 2] Radical Annulation of Aryl Isothiocyanates with 2-Cyano-Substituted Aryl Radicals

A novel cascade radical reaction is described involving aryl isothiocyanates and 2-cyanoaryl radicals. The mechanism entails the formation of an alpha-(arylthio)imidoyl radical, a 5-exo-dig cyclization onto a cyano group, and a final 6-membered ring closure of an iminyl radical. The competitive 5-membered spiro-cyclization of the iminyl, leading to an isomeric product, was only observed in the case of a disubstituted aryl isothiocyanate. The whole process involves a rare example of [3 + 2] radical annulation and allows the one-pot synthesis of tetracondensed nitrogen heterocycles in good yields.     

Generation and intramolecular reactivity of acyl radicals from alkynylthiol esters under reducing tin-free conditions

[reaction: see text] The radical chain reaction of benzenethiol with alkynylthiol esters provides a new, valuable protocol for the tin-free generation of acyl radicals that arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals.     

|\epsilon|-Near-zero materials in the near-infrared

We consider a mixture of metal-coated quantum dots dispersed in a polymer matrix and, using a modified version of the standard Maxwell-Garnett mixing rule, we prove that the mixture parameters (particles radius, quantum dots gain, etc.) can be chosen so that the effective medium permittivity has an absolute value very close to zero in the near-infrared, i.e. $|{\rm Re}(\epsilon)| \ll 1$ and $|{\rm Im}(\epsilon)| \ll 1$ at the same near-infrared wavelength. Resorting to full-wave simulations, we investigate the accuracy of the effective medium predictions and we relate their discrepancy with rigorous numerical results to the fact that $|\epsilon| \ll 1$ is a critical requirement. We show that a simple method for reducing this discrepancy, and hence for achieving a prescribed and very small value of $|\epsilon|, $ consists in a subsequent fine-tuning of the nanoparticles volume filling fraction.     

Wave scattering functions and their application to multiple scattering problems

Scattering functions arise naturally in standard treatments of the effects of a material object or surface embedded in a uniform field. The most commonly used scattering function describes the far-field modulation imparted at large distances to a spherical wavefront eminating from the scatterer. The purpose of this is to develop the properties of the spectrum of scattered plane waves as an exact generalized scattering function. The linearity of the wave equations guarantees that such a representation exists; moreover, it is possible to derive the generalized scattering function from the far-field scattering function by analytic continuation. Although these properties are known, recent theoretical developments have motivated us to reexplore the interrelations among the far-field scattering function, the Green's function and various forms of the generalized scattering function as well as the symmetry properties of the generalized scattering function imposed by reciprocity. For multiple-scattering objects that can be separated by parallel planes, a system of difference equations is developed that fully accommodates the mutual interaction among the scatterers. The mutual interaction equations were developed earlier, but we show here that they can be transformed into the form that would be obtained by using the Foldy-Lax-Twersky formalism. This reinforces the equivalence between wave-space and configuration space formulations of the scattering problems.