Synthesis of highly substituted allenylsilanes by alkylidenation of silylketenes

BACKGROUND: Allenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes prepared through rhodium(II)-mediated rearrangement of silylated diazoketones. RESULTS: A range of novel 1,3-disubstituted and 1,3,3-trisubstituted allenylsilanes were prepared using stabilised and semi-stabilised ylides. Alkylidenation with non-stabilised phosphorus ylides was not viable, but the use of titanium-based methylenating reagents was successful, allowing access to 1-substituted allenylsilanes. CONCLUSION: Many novel allenylsilanes may be accessed by alkylidenation of substituted silylketenes. Importantly, for the first time, simple methylenation of silylketenes has been achieved using titanium carbenoid-based reagents

Inter- and intramolecular Diels-Alder/retro-Diels-Alder reactions of 4-silylated oxazoles

4-Silylated oxazoles have been shown to undergo inter- and intramolecular Diels-Alder/retro-Diels-Alder reactions with electron-poor alkynes to generate polysubstituted furans. The ease of synthesis of the requisite oxazoles by the rhodium-catalysed condensation of nitriles with silylated diazoacetate greatly increases the scope of this reaction

Synthesis and characterisation of novel fluorescent imides by a rhodium(III)-catalysed C-H activation/annulation cascade

Regioselective rhodium(III)-catalysed C-H activation/annulation of O-pivaloyl benzoylhydroxamates with ortho-alkynylbenzoate esters facilitates the rapid preparation of a novel class of fluorophores based on the isoindolo[2,1-b]isoquinoline-5,7-dione core. The photophysical, electrochemical and coordination properties of these novel structures are investigated

GG-Strands

A $G$-strand is a map $g(t,{s}):\,\mathbb{R}\times\mathbb{R}\to G$ for a Lie group $G$ that follows from Hamilton's principle for a certain class of $G$-invariant Lagrangians. The SO(3)-strand is the $G$-strand version of the rigid body equation and it may be regarded physically as a continuous spin chain. Here, $SO(3)_K$-strand dynamics for ellipsoidal rotations is derived as an Euler-Poincar\'e system for a certain class of variations and recast as a Lie-Poisson system for coadjoint flow with the same Hamiltonian structure as for a perfect complex fluid. For a special Hamiltonian, the $SO(3)_K$-strand is mapped into a completely integrable generalization of the classical chiral model for the SO(3)-strand. Analogous results are obtained for the $Sp(2)$-strand. The $Sp(2)$-strand is the $G$-strand version of the $Sp(2)$ Bloch-Iserles ordinary differential equation, whose solutions exhibit dynamical sorting. Numerical solutions show nonlinear interactions of coherent wave-like solutions in both cases. ${\rm Diff}(\mathbb{R})$-strand equations on the diffeomorphism group $G={\rm Diff}(\mathbb{R})$ are also introduced and shown to admit solutions with singular support (e.g., peakons).Comment: 35 pages, 5 figures, 3rd version. To appear in J Nonlin Sc

The Relation Between the Surface Brightness and the Diameter for Galactic Supernova Remnants

In this work, we have constructed a relation between the surface brightness ($\Sigma$) and diameter (D) of Galactic C- and S-type supernova remnants (SNRs). In order to calibrate the $\Sigma$-D dependence, we have carefully examined some intrinsic (e.g. explosion energy) and extrinsic (e.g. density of the ambient medium) properties of the remnants and, taking into account also the distance values given in the literature, we have adopted distances for some of the SNRs which have relatively more reliable distance values. These calibrator SNRs are all C- and S-type SNRs, i.e. F-type SNRs (and S-type SNR Cas A which has an exceptionally high surface brightness) are excluded. The Sigma-D relation has 2 slopes with a turning point at D=36.5 pc: $\Sigma$(at 1 GHz)=8.4$^{+19.5}_{-6.3}$$\times10^{-12}$ D$^{{-5.99}^{+0.38}_{-0.33}}$ Wm$^{-2}$Hz$^{-1}$ster$^{-1}$ (for $\Sigma$$\le3.7\times10^{-21}$ Wm$^{-2}$Hz$^{-1}$ster$^{-1}$ and D$\ge$36.5 pc) and $\Sigma$(at 1 GHz)=2.7$^{+2.1}_{-1.4}$$\times$ 10$^{-17}$ D$^{{-2.47}^{+0.20}_{-0.16}}$ Wm$^{-2}$Hz$^{-1}$ster$^{-1}$ (for $\Sigma$$>3.7\times10^{-21}$ Wm$^{-2}$Hz$^{-1}$ster$^{-1}$ and D$<$36.5 pc). We discussed the theoretical basis for the $\Sigma$-D dependence and particularly the reasons for the change in slope of the relation were stated. Added to this, we have shown the dependence between the radio luminosity and the diameter which seems to have a slope close to zero up to about D=36.5 pc. We have also adopted distance and diameter values for all of the observed Galactic SNRs by examining all the available distance values presented in the literature together with the distances found from our $\Sigma$-D relation.Comment: 45 pages, 2 figures, accepted for publication in Astronomical and Astrophysical Transaction

Search for H→γγ produced in association with top quarks and constraints on the Yukawa coupling between the top quark and the Higgs boson using data taken at 7 TeV and 8 TeV with the ATLAS detector

A search is performed for Higgs bosons produced in association with top quarks using the diphoton decay mode of the Higgs boson. Selection requirements are optimized separately for leptonic and fully hadronic final states from the top quark decays. The dataset used corresponds to an integrated luminosity of 4.5 fb−14.5 fb−1 of proton–proton collisions at a center-of-mass energy of 7 TeV and 20.3 fb−1 at 8 TeV recorded by the ATLAS detector at the CERN Large Hadron Collider. No significant excess over the background prediction is observed and upper limits are set on the tt¯H production cross section. The observed exclusion upper limit at 95% confidence level is 6.7 times the predicted Standard Model cross section value. In addition, limits are set on the strength of the Yukawa coupling between the top quark and the Higgs boson, taking into account the dependence of the tt¯H and tH cross sections as well as the H→γγ branching fraction on the Yukawa coupling. Lower and upper limits at 95% confidence level are set at −1.3 and +8.0 times the Yukawa coupling strength in the Standard Model

Search for strong gravity in multijet final states produced in pp collisions at √s=13 TeV using the ATLAS detector at the LHC

A search is conducted for new physics in multijet final states using 3.6 inverse femtobarns of data from proton-proton collisions at √s = 13TeV taken at the CERN Large Hadron Collider with the ATLAS detector. Events are selected containing at least three jets with scalar sum of jet transverse momenta (HT) greater than 1TeV. No excess is seen at large HT and limits are presented on new physics: models which produce final states containing at least three jets and having cross sections larger than 1.6 fb with HT > 5.8 TeV are excluded. Limits are also given in terms of new physics models of strong gravity that hypothesize additional space-time dimensions

Operation and performance of the ATLAS semiconductor tracker

The semiconductor tracker is a silicon microstrip detector forming part of the inner tracking system of the ATLAS experiment at the LHC. The operation and performance of the semiconductor tracker during the first years of LHC running are described. More than 99% of the detector modules were operational during this period, with an average intrinsic hit efficiency of (99.74±0.04)%. The evolution of the noise occupancy is discussed, and measurements of the Lorentz angle, δ-ray production and energy loss presented. The alignment of the detector is found to be stable at the few-micron level over long periods of time. Radiation damage measurements, which include the evolution of detector leakage currents, are found to be consistent with predictions and are used in the verification of radiation background simulations

Measurement of the correlation between flow harmonics of different order in lead-lead collisions at √sNN = 2.76 TeV with the ATLAS detector

Correlations between the elliptic or triangular flow coefficients vm (m=2 or 3) and other flow harmonics vn (n=2 to 5) are measured using √sNN=2.76 TeV Pb+Pb collision data collected in 2010 by the ATLAS experiment at the LHC, corresponding to an integrated luminosity of 7 μb−1. The vm−vn correlations are measured in midrapidity as a function of centrality, and, for events within the same centrality interval, as a function of event ellipticity or triangularity defined in a forward rapidity region. For events within the same centrality interval, v3 is found to be anticorrelated with v2 and this anticorrelation is consistent with similar anticorrelations between the corresponding eccentricities, ε2 and ε3. However, it is observed that v4 increases strongly with v2, and v5 increases strongly with both v2 and v3. The trend and strength of the vm−vn correlations for n=4 and 5 are found to disagree with εm−εn correlations predicted by initial-geometry models. Instead, these correlations are found to be consistent with the combined effects of a linear contribution to vn and a nonlinear term that is a function of v22 or of v2v3, as predicted by hydrodynamic models. A simple two-component fit is used to separate these two contributions. The extracted linear and nonlinear contributions to v4 and v5 are found to be consistent with previously measured event-plane correlations

Fiducial and differential cross sections of Higgs boson production measured in the four-lepton decay channel in pp collisions at √s = 8 TeV with the ATLAS detector

Measurements of fiducial and differential cross sections of Higgs boson production in the H→ZZ∗ → 4ℓ decay channel are presented. The cross sections are determined within a fiducial phase space and corrected for detection efficiency and resolution effects. They are based on 20.3 fb−¹ of pp collision data, produced at √s = 8 TeV centre-of-mass energy at the LHC and recorded by the ATLAS detector. The differential measurements are performed in bins of transverse momentum and rapidity of the four-lepton system, the invariant mass of the subleading lepton pair and the decay angle of the leading lepton pair with respect to the beam line in the four-lepton rest frame, as well as the number of jets and the transverse momentum of the leading jet. The measured cross sections are compared to selected theoretical calculations of the Standard Model expectations. No significant deviation from any of the tested predictions is found