New palladium-catalyzed approaches to heterocycles and carbocycles

The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields.;The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products.;Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields.;Novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.;A relatively efficient synthesis of cyclopropanes has been developed using palladium-catalyzed C-H activation chemistry, in which two new carbon-carbon bonds are formed in a single step. This method involves the palladium-catalyzed activation of relatively unreactive C-H bonds, and provides a very efficient way to synthesize cyclopropapyrrolo[1,2-a]indoles, analogues of the mitomycin antibiotics

Aryl to Aryl Palladium Migration in the Heck and Suzuki Coupling of o-Halobiaryls

A novel 1,4-palladium migration between the o- and o‘-positions of biaryls has been observed in organopalladium intermediates derived from o-halobiaryls. The organopalladium intermediates generated by this migration have been trapped either by a Heck reaction employing ethyl acrylate or by Suzuki cross-coupling using arylboronic acids. This palladium migration can be activated or deactivated by choosing the appropriate reaction conditions. Chemical and computational evidence supports the presence of an equilibrium that correlates with the C−H acidity of the available arene positions

Efficiency and timing performance of the MuPix7 high-voltage monolithic active pixel sensor

The MuPix7 is a prototype high voltage monolithic active pixel sensor with 103 times 80 um2 pixels thinned to 64 um and incorporating the complete read-out circuitry including a 1.25 Gbit/s differential data link. Using data taken at the DESY electron test beam, we demonstrate an efficiency of 99.3% and a time resolution of 14 ns. The efficiency and time resolution are studied with sub-pixel resolution and reproduced in simulations.Comment: 7 pages, 13 figures, submitted to Nucl.Instr.Meth.

New palladium-catalyzed approaches to heterocycles and carbocycles

The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields.;The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products.;Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields.;Novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.;A relatively efficient synthesis of cyclopropanes has been developed using palladium-catalyzed C-H activation chemistry, in which two new carbon-carbon bonds are formed in a single step. This method involves the palladium-catalyzed activation of relatively unreactive C-H bonds, and provides a very efficient way to synthesize cyclopropapyrrolo[1,2-a]indoles, analogues of the mitomycin antibiotics.</p

Vers la détermination de la hiérarchie de masse des neutrinos avec l'expérience JUNO

The JUNO experiment is a multi-purpose liquid scintillator neutrino experiment with the main objective of determining the neutrino mass hierarchy (nuMH) with a significance better than 3sigma. To achieve this goal, it is crucial that JUNO has an unprecedented energy resolution of 3% at 1 MeV. Therefore, the JUNO Central Detector (CD) will be built with 20000 ton high transparency liquid scintillator and high photomultiplier tube (PMT) photocathode coverage of 78%, which is provided by 18000 20"-PMTs (LPMTs) and 25000 3"-PMTs (SPMTs). At the same time, the background induced by atmospheric muons should be vetoed by using reconstructed muon tracks. The Top Tracker (TT) is a muon tracker installed on top of the CD for precise muon tracking.This thesis details firstly the optimisation of the LPMT and the SPMT systems, which are directly related to the antineutrino calorimetry. New designs of light concentrator tailored for the JUNO LPMT are studied in order to verify their performance on increasing the JUNO photoelectron yield. By comparing different configurations, the relation between the SPMT system performance and the non-uniform distribution of the SPMT emplacements is studied, and the scheme used for cabling between SPMTs and their Under Water Boxes (UWBs) is studied to ensure a minimal performance degradation in case of UWB failure.Afterwards, this thesis reports on the design and optimisation of the TT trigger algorithms. Due to the background induced by natural radioactivity in the JUNO cavern, the TT cannot work correctly without a trigger system. The results show that a 2-level trigger with the optimised trigger algorithm is effective for the background suppression and thus a muon detection efficiency of 93% can be achieved.A discussion about the TT contribution to the suppression and the measurement of the atmospheric muon-induced background, is also included.L'expérience JUNO est une expérience basée sur un détecteur à scintillateur liquide ayant pour objectif principal de déterminer la hiérarchie de masse des neutrinos. JUNO atteindra une sensibilité de trois écarts standards en 6 ans, avec une résolution en énergie sans précédent, meilleure que 3% à 1MeV. Le détecteur central de JUNO est un détecteur à scintillateur liquide de 20 kilotonnes, construit avec une couverture de photocathode élevée (78%) et une bonne transparence. La couverture de photocathode est assurée par 18000 photomultiplicateurs de 20 pouces et 25000 de 3 pouces, ce qui permet d'atteindre un rendement d'environ 1200 photoélectrons par MeV. Malgré les 700m d'épaisseur de roche protégeant le détecteur des rayonnements cosmiques, le bruit de fond induit par les muons atmosphériques est toujours considéré comme non négligeable par rapport au signal attendu pour la détermination de la hiérarchie de masse. Pour faire face à ce bruit de fond, un détecteur appelé "Top Tracker" permet d'améliorer la détection de ces muons. Cette thèse concerne les travaux d'optimisation pour cette expérience actuellement en cours de construction, et dont les prises de données commenceront en 2021.Pour les photomultiplicateurs de 20 pouces, deux nouvelles géométries de concentrateurs de lumière sont étudiées afin de vérifier leurs performances pour augmenter le rendement photoélectronique et donc la résolution en énergie de JUNO. La distribution spatiale et le schéma de câblage des photomultiplicateurs de 3 pouces font aussi l'objet d'études pour assurer une performance optimale du système.Cette thèse aborde ensuite la conception du système de déclenchement du Top Tracker. En effet, ce détecteur doit posséder un tel système pour rejeter les signaux produits par la radioactivité naturelle dans la caverne. Les résultats montrent qu'un système à 2 niveaux doté d'algorithmes optimisés est efficace pour la suppression de ces signaux et qu'il est ainsi possible d'obtenir une efficacité de détection des muons de 93%. Une discussion sur la contribution du Top Tracker à la suppression et à la mesure du bruit de fond induit par les muons atmosphériques est également incluse

Current status of JUNO Top Tracker

International audienceThe JUNO experiment is a multi-purpose antineutrino oscillation experiment with the main objective of determining the neutrino mass hierarchy with a sensitivity better than 3$\sigma$, which requires JUNO to have an energy resolution better than 3% at 1MeV. The JUNO Central Detector, a 20 kton liquid scintillator detector, will be built with high PMT photocathode coverage and good transparency for this purpose.Despite the 700m overburden, the atmospheric muon-induced background is still estimated to be non negligible compared to the expected signal for the neutrino mass hierarchy determination. A veto system was designed for muon detection to tag and to suppress this background. It consists of two subsystems: the Top Tracker and the Water Cherenkov Detector. The Top Tracker is a 3-layer muon tracker covering about 60% of the top surface above the JUNO water pool and will provide precise tracking for atmospheric muons. These well reconstructed muons are essential in the veto strategy for rejecting cosmogenic isotope background. Combining the muon information from the Top Tracker and the Water Cherenkov Detector, most of the atmospheric muon-induced background can be removed.This proceeding will present the current status and the expected performance of the JUNO Top Tracker