Rearrangement of a Transient Gold Vinylidene into Gold Carbenes

The gold acetylide complex 20 endowed with a biaryl backbone provides opportunities for a study on the formation and fate of gold vinylidenes. Although the formyl group in 20 is not sufficiently electrophilic to get attacked by the acetylide in proximity, its activation with TBSOTf (TBSOTf=tert-butyldimethylsilyl trifluoromethanesulfonate) at low temperature triggered instantaneous formation of a gold vinylidene (21). This metastable species evolved into the cationic gold carbene complex 22 bearing a phenanthrene unit and a hydroxyl group at the aurated center; the recorded data suggest that this product might be better viewed as an acylgold species protonated by triflic acid. The use of [Me3O⋅BF4] as the activating agent led to formation of the analogous Fischer-type carbene 24, whereas replacement of gold by the [CpRu(PPh3)2]+ fragment allowed the ruthenium vinylidene 27 to be isolated, which closely resembles the proposed gold intermediate 21. The starting gold complex 20, the derived products 22 and 24, as well as vinylidene 27 were characterized by X-ray diffraction

On the discovery and development of tandem 1,4- and 1,2-addition of phosphites to 1-azadienes

Over the past 15 years we have developed a one-step protocol for the synthesis of 3-phosphonylated aminophosphonates from alpha,beta-unsaturated imines through tandem 1,4-1,2-phosphite addition. This account covers the initial development, mechanistic implications of using different phosphite nucleophiles and the expansion towards oximes, hydrazones and unsaturated imines included in aromatic sextets, e. g. quinolines, phenanthrolines and napthyridines

Direct regio- and diastereoselective diphosphonylation of cyclic enamines : one-pot synthesis of α,α′-bis(diphenylphosphoryl)- and α,α′-bis(diphenylphosphorothioyl)cycloalkanones

A straightforward regio- and diastereoselective process has been developed for the synthesis of unprecedented symmetrical trans-alpha,alpha '-bis(diphenylphosphoryl)- and alpha,alpha '-bis(diphenylphosphorothioyl)cycloalkanones, through the reaction of cyclic enamines with excess P-chlorodiphenylphosphine in the presence of triethylamine, followed by oxidation or sulfurization and hydrolytic workup

JB-300: An advanced medium size transport for 2005

In the fall of 1992, the TAC Team was presented with a Request for Proposal (PFP) for a mid-size (250-350 passenger) commercial transport. The aircraft was to be extremely competitive in the areas of passenger comfort, performance, and economic aspects. Through the use of supercritical airfoils, a technologically advanced Very High By-pass Ratio (VHBR) turbofan engine, a low overall drag configuration, a comparable interior layout, and mild use of composites, the JB-300 offers an economically viable choice to the airlines. The cents per passenger mile of the JB-300 is 1.76, which is considerably lower than current aircraft in the same range. Overall, the JB-300 is a technologically advanced aircraft, which will meet the demands of the 21st century

La responsabilisation des détenus dans les nouveaux établissements pénitentiaires belges : étude empirique de la prison de Marche-en-Famenne

La notion de responsabilisation connait plusieurs acceptations qui s’accordent autour de l’idée de processus dynamique visant à assumer ses dires, ses actes, ses responsabilités. La peine privative de liberté endosse quant à elle diverses fonctions traditionnellement reconnues. Parmi elles, l’idée que la sanction se doit de préparer la personne incarcérée à se réinsérer au sein de la société qu’il a offensée gagne peu à peu en popularité tant auprès des décideurs politiques qu'au sein de l’opinion publique. Dans cette optique, la responsabilisation intègre ce processus de civilisation en tant qu’objectif de la détention. Ce travail se penche donc sur la place réelle de cette notion au sein des prisons les plus jeunes du pays au travers de celle de Marche-en-Famenne qui, par son projet innovant, tend à favoriser la responsabilisation des sujets détenus. L’analyse des dispositifs instaurés au sein de cette dernière offre un cadre de réflexion contextualisé et établit une base de réflexion permettant d’évaluer le bien-fondé des régimes pénitentiaires majoritairement appliqués dans le Royaume sous l’angle de la responsabilisation des détenus.Master [120] en criminologie, Université catholique de Louvain, 201