Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

A continuous process strategy has been developed for the preparation of α-thio-β chloroacrylamides, a class of highly versatile synthetic intermediates. Flow platforms to generate the α-chloroamide and α-thioamide precursors were successfully adopted, progressing from the previously employed batch chemistry, and in both instances afford a readily scalable methodology. The implementation of the key α-thio-β-chloroacrylamide casade as a continuous flow reaction on a multi-gram scale is described, while the tuneable nature of the cascade, facilitated by continuous processing, is highlighted by selective generation of established intermediates and byproducts

Uncovering the Orbit of the Hercules Dwarf Galaxy

We present new chemo--kinematics of the Hercules dwarf galaxy based on Keck II-- DEIMOS spectroscopy. Our 21 confirmed members have a systemic velocity of $v_{\mathrm{Herc}}=46.4\pm1.3$ kms$^{-1}$ and a velocity dispersion $\sigma_{v,\mathrm{Herc}}=4.4^{+1.4}_{-1.2}$ kms$^{-1}$. From the strength of the Ca II triplet, we obtain a metallicity of [Fe/H]= $-2.48\pm0.19$ dex and dispersion of $\sigma_{\rm{[Fe/H]}}= 0.63^{+0.18}_{-0.13}$ dex. This makes Hercules a particularly metal--poor galaxy, placing it slightly below the standard mass--metallicity relation. Previous photometric and spectroscopic evidence suggests that Hercules is tidally disrupting and may be on a highly radial orbit. From our identified members, we measure no significant velocity gradient. By cross--matching with the second \textit{Gaia} data release, we determine an uncertainty--weighted mean proper motion of $\mu_{\alpha}^*=\mu_{\alpha}\cos(\delta)=-0.153\pm{0.074}$ mas yr$^{-1}$, $\mu_{\delta}=-0.397\pm0.063$ mas yr$^{-1}$. This proper motion is slightly misaligned with the elongation of Hercules, in contrast to models which suggest that any tidal debris should be well aligned with the orbital path. Future observations may resolve this tension.Comment: Submitted to MNRAS. 17 pages, 14 figure

Bloch-Nordsieck violating electroweak corrections to inclusive TeV scale hard processes

We point out that, since the colliders initial states (e+ e-,p p, p pbar, ... ) carry a definite nonabelian flavor, electroweak radiative corrections to inclusive hard cross sections at the TeV scale are affected by peculiar Bloch-Nordsieck violating double logs. We recall the setup of soft cancellation theorems, and we analyze the magnitude of the noncancelling terms in the example of electron - positron annihilation into hadrons.Comment: Minor typos corrected, references added. Final version to appear on Phys. Rev. Let

Generation of tosyl azide in continuous flow using an azide resin, and telescoping with diazo transfer and rhodium acetate-catalyzed O-H insertion.

Generation of tosyl azide 12 in acetonitrile in flow under water-free conditions using an azide resin and its use in diazo transfer to a series of aryl acetates are described. Successful telescoping with a rhodium acetate-catalyzed O-H insertion has been achieved, thereby transforming the aryl acetate 8 to a-hydroxy ester 10, a key intermediate in the synthesis of clopidogrel 11, without requiring isolation or handling of either tosyl azide 12 or a-aryl-a-diazoacetate 9, or indeed having significant amounts of either present at any point. Significantly, the solution of a-diazo ester 9 was sufficiently clean to progress directly to the rhodium acetate-catalyzed step without any detrimental impact on the efficiency of the O-H insertion. In addition, the rhodium acetate-catalyzed O-H insertion process is cleaner in flow than under traditional batch conditions. Use of the azide resin offers clear safety advantages and, in addition, this approach complements earlier protocols for the generation of tosyl azide 12 in flow; this protocol is especially useful with less acidic substrates

Taming tosyl azide: the development of a scalable continuous diazo transfer process

Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diazo transfer reactions tosyl azide was generated and used in a telescoped flow process, to mitigate the risks associated with handling potentially explosive reagents on scale. The in situ formed tosyl azide was used to rapidly perform diazo transfer to a range of acceptors, including beta-ketoesters, beta-ketoamides, malonate esters and beta-ketosulfones. An effective in-line quench of sulfonyl azides was also developed, whereby a sacrificial acceptor molecule ensured complete consumption of any residual hazardous diazo transfer reagent. The telescoped diazo transfer process with in-line quenching was used to safely prepare over 21 g of an alpha-diazocarbonyl in > 98% purity without any column chromatography

Exploiting continuous processing for challenging diazo transfer and telescoped copper-catalyzed asymmetric transformations

Generation and use of triflyl azide in flow enables efficient synthesis of a range of α-diazocarbonyl compounds, including α-diazoketones, α-diazoamides, and an α-diazosulfonyl ester, via both Regitz-type diazo transfer and deacylative/debenzoylative diazo-transfer processes with excellent yields and offers versatility in the solvent employed, in addition to addressing the hazards associated with handling of this highly reactive sulfonyl azide. Telescoping the generation of triflyl azide and diazo-transfer process with highly enantioselective copper-mediated intramolecular aromatic addition and C–H insertion processes demonstrates that the reaction stream containing the α-diazocarbonyl compound can be obtained in sufficient purity to pass directly over the immobilized copper bis(oxazoline) catalyst without detrimentally impacting the catalyst enantioselectivity

Single hadron response measurement and calorimeter jet energy scale uncertainty with the ATLAS detector at the LHC

The uncertainty on the calorimeter energy response to jets of particles is derived for the ATLAS experiment at the Large Hadron Collider (LHC). First, the calorimeter response to single isolated charged hadrons is measured and compared to the Monte Carlo simulation using proton-proton collisions at centre-of-mass energies of sqrt(s) = 900 GeV and 7 TeV collected during 2009 and 2010. Then, using the decay of K_s and Lambda particles, the calorimeter response to specific types of particles (positively and negatively charged pions, protons, and anti-protons) is measured and compared to the Monte Carlo predictions. Finally, the jet energy scale uncertainty is determined by propagating the response uncertainty for single charged and neutral particles to jets. The response uncertainty is 2-5% for central isolated hadrons and 1-3% for the final calorimeter jet energy scale.Comment: 24 pages plus author list (36 pages total), 23 figures, 1 table, submitted to European Physical Journal

Exploiting the continuous in situ generation of mesyl azide for use in a telescoped process

The hazardous diazo transfer reagent mesyl azide has been safely generated and used in situ for continuous diazo transfer as part of an integrated synthetic process with an embedded safety quench. Diazo transfer to β‐keto esters and a β‐ketosulfone was successful. In‐line phase separation, by means of a continuous liquid–liquid separator enabled direct telescoping with a thermal Wolff rearrangement. 1

Measurements of Higgs boson production and couplings in diboson final states with the ATLAS detector at the LHC

Measurements are presented of production properties and couplings of the recently discovered Higgs boson using the decays into boson pairs, H →γ γ, H → Z Z∗ →4l and H →W W∗ →lνlν. The results are based on the complete pp collision data sample recorded by the ATLAS experiment at the CERN Large Hadron Collider at centre-of-mass energies of √s = 7 TeV and √s = 8 TeV, corresponding to an integrated luminosity of about 25 fb−1. Evidence for Higgs boson production through vector-boson fusion is reported. Results of combined fits probing Higgs boson couplings to fermions and bosons, as well as anomalous contributions to loop-induced production and decay modes, are presented. All measurements are consistent with expectations for the Standard Model Higgs boson

Standalone vertex finding in the ATLAS muon spectrometer

A dedicated reconstruction algorithm to find decay vertices in the ATLAS muon spectrometer is presented. The algorithm searches the region just upstream of or inside the muon spectrometer volume for multi-particle vertices that originate from the decay of particles with long decay paths. The performance of the algorithm is evaluated using both a sample of simulated Higgs boson events, in which the Higgs boson decays to long-lived neutral particles that in turn decay to bbar b final states, and pp collision data at √s = 7 TeV collected with the ATLAS detector at the LHC during 2011