Epoxides: Small Rings to Play with under Asymmetric Organocatalysis

Optically pure epoxides are recognized as highly valuable products and key intermediates, useful in different areas from pharmaceutical and agrochemical industries to natural product synthesis and materials science. The predictable fate of the ring-opening process, in terms of stereoselectivity and often of regioselectivity, enables useful functional groups to be installed at vicinal carbon atoms in a desired manner. In this way, products of widespread utility either for synthetic applications or as final products can be obtained. The advent of asymmetric organocatalysis provided a new convenient tool, not only for their preparation but also for the elaboration of this class of heterocycles. In this review, we focus on recent developments of stereoselective organocatalytic ring-opening reactions of meso-epoxides, kinetic resolution of racemic epoxides, and Meinwald-type rearrangement. Examples of asymmetric organocatalytic processes toward specific synthetic targets, which include ring opening of an epoxide intermediate, are also illustrated

Chiral organocatalysts mediated asymmetric oxyfunctionalization and tandem reaction

2013 - 2014Asymmetric organocatalysis is a new rapidly growing field whose huge potential is becoming more and more evident.This PhD project has been conceived and developed in the context of non-covalent organocatalysis. The aim of this work has been to design, plan and develop new organocatalytic methodologies for the synthesis of optically active, densely functionalized, organic molecules whose functional groups are susceptible to further manipulation. The target molecules represent important motifs present in many biologically active natural and non-natural substances. The catalysts used are small chiral organic molecules, in particular the attention has been focused on bifunctional organocatalysts. The main features of the catalysts are their non-toxicity, stability to air and moisture and the ability to work under mild conditions that make them convenient tools in organic chemistry. These promoters are able to synergistically activate both the electrophile and the nucleophile through multiple hydrogen-bonding interactions provided by their acid and basic groups with the reactive groups of the reagents. The best-performing chiral scaffold of the bifunctional organocatalysts, employed in the methodologies herein developed, has been selected screening the activity of previously reported promoters such as ureas, thioureas, squaramides, amino alcohols. However, the design and synthesis of new optically pure bifunctional organocatalysts, modifying the chiral backbone and by tuning their stereoelectronic features, has been one of the objectives of this doctoral project. The stereoselective construction of a quaternary stereocentre, especially when it is an all-carbon quaternary stereocentre, is one of the most difficult goals in organic synthesis due to the steric congestion imposed by the four attached substituents. In this project, the synthesis of challenging molecules, bearing quaternary stereocentres in their structure, has been accomplished... [edited by author]XIII n.s

Correction: catalytic enantioselective synthesis of α-nitroepoxides via aminolytic kinetic resolution

Correction for 'Catalytic enantioselective synthesis of α-nitroepoxides via aminolytic kinetic resolution' by Sara Meninno et al., Catal. Sci. Technol., 2015, 5, 124–128

Azimuthal anisotropy of charged jet production in root s(NN)=2.76 TeV Pb-Pb collisions

We present measurements of the azimuthal dependence of charged jet production in central and semi-central root s(NN) = 2.76 TeV Pb-Pb collisions with respect to the second harmonic event plane, quantified as nu(ch)(2) (jet). Jet finding is performed employing the anti-k(T) algorithm with a resolution parameter R = 0.2 using charged tracks from the ALICE tracking system. The contribution of the azimuthal anisotropy of the underlying event is taken into account event-by-event. The remaining (statistical) region-to-region fluctuations are removed on an ensemble basis by unfolding the jet spectra for different event plane orientations independently. Significant non-zero nu(ch)(2) (jet) is observed in semi-central collisions (30-50% centrality) for 20 <p(T)(ch) (jet) <90 GeV/c. The azimuthal dependence of the charged jet production is similar to the dependence observed for jets comprising both charged and neutral fragments, and compatible with measurements of the nu(2) of single charged particles at high p(T). Good agreement between the data and predictions from JEWEL, an event generator simulating parton shower evolution in the presence of a dense QCD medium, is found in semi-central collisions. (C) 2015 CERN for the benefit of the ALICE Collaboration. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).Peer reviewe

Performance of the ALICE experiment at the CERN LHC

ALICE is the heavy-ion experiment at the CERN Large Hadron Collider. The experiment continuously took data during the first physics campaign of the machine from fall 2009 until early 2013, using proton and lead-ion beams. In this paper we describe the running environment and the data handling procedures, and discuss the performance of the ALICE detectors and analysis methods for various physics observables

Forward-central two-particle correlations in p-Pb collisions at root s(NN)=5.02 TeV

Two-particle angular correlations between trigger particles in the forward pseudorapidity range (2.5 2GeV/c. (C) 2015 CERN for the benefit of the ALICE Collaboration. Published by Elsevier B. V.Peer reviewe

Event-shape engineering for inclusive spectra and elliptic flow in Pb-Pb collisions at root(NN)-N-S=2.76 TeV

Peer reviewe

Multiplicity dependence of jet-like two-particle correlation structures in p-Pb collisions at 1asNN=5.02 TeV

Two-particle angular correlations between unidentified charged trigger and associated particles are measured by the ALICE detector in p\u2013Pb collisions at a nucleon\u2013nucleon centre-of-mass energy of 5.02 TeV. The transverse-momentum range 0.7 < pT,assoc < pT,trig < 5.0 GeV/c is examined, to include correlations induced by jets originating from low momentum-transfer scatterings (minijets). The correlations expressed as associated yield per trigger particle are obtained in the pseudorapidity range |\u3b7| < 0.9. The near-side long-range pseudorapidity correlations observed in high-multiplicity p\u2013Pb collisions are subtracted from both near-side short-range and away-side correlations in order to remove the non-jet-like components. The yields in the jet-like peaks are found to be invariant with event multiplicity with the exception of events with low multiplicity. This invariance is consistent with the particles being produced via the incoherent fragmentation of multiple parton\u2013parton scatterings, while the yield related to the previously observed ridge structures is not jet-related. The number of uncorrelated sources of particle production is found to increase linearly with multiplicity, suggesting no saturation of the number of multi-parton interactions even in the highest multiplicity p\u2013Pb collisions. Further, the number scales only in the intermediate multiplicity region with the number of binary nucleon\u2013nucleon collisions estimated with a Glauber Monte-Carlo simulation

Elliptic flow of muons from heavy-flavour hadron decays at forward rapidity in Pb-Pb collisions at root s(NN)=2.76TeV

The elliptic flow, v(2), of muons from heavy-flavour hadron decays at forward rapidity (2.5 <y <4) is measured in Pb-Pb collisions at root s(NN)= 2.76TeVwith the ALICE detector at the LHC. The scalar product, two- and four-particle Q cumulants and Lee-Yang zeros methods are used. The dependence of the v(2) of muons from heavy-flavour hadron decays on the collision centrality, in the range 0-40%, and on transverse momentum, p(T), is studied in the interval 3 <p(T)<10 GeV/c. A positive v(2) is observed with the scalar product and two-particle Q cumulants in semi-central collisions (10-20% and 20-40% centrality classes) for the p(T) interval from 3 to about 5GeV/c with a significance larger than 3 sigma, based on the combination of statistical and systematic uncertainties. The v(2) magnitude tends to decrease towards more central collisions and with increasing pT. It becomes compatible with zero in the interval 6 <p(T)<10 GeV/c. The results are compared to models describing the interaction of heavy quarks and open heavy-flavour hadrons with the high-density medium formed in high-energy heavy-ion collisions. (C) 2015 CERN for the benefit of the ALICE Collaboration. Published by Elsevier B.V.Peer reviewe