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.     

An Application of a Theorem of Sheila Brenner for Hochschild Extension Algebras of a Truncated Quiver Algebra

Let A be a truncated quiver algebra over an algebraically closed field such that any oriented cycle in the ordinary quiver of A is zero in A. We give the number of the indecomposable direct summands of the middle term of an almost split sequence for a class of Hochschild extension algebras of A by the standard duality module D(A).

     

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.