Microwave-assisted synthesis of azetidines in aqueous media

Simple azetidines are synthesized in good to excellent yields and high purity via cyclization of 3-(ammonio)propyl sulfates derived from primary amines and the cyclic sulfate of 1,3-propanediol. A feature of this methodology includes the accelerated synthesis of azetidines in water under the influence of microwave-assisted heating.     

Direct top-quark width measurement at CDF

We present a measurement of the top-quark width in the lepton+jets decay channel of tt events produced in p p collisions at Fermilab's Tevatron collider and collected by the CDF II detector. From a data sample corresponding to 4.3 fb(-1) of integrated luminosity, we identify 756 candidate events. The top-quark mass and the mass of the hadronically decaying W boson that comes from the top-quark decay are reconstructed for each event and compared with templates of different top-quark widths (Γ(t)) and deviations from nominal jet energy scale (Δ(JES)) to perform a simultaneous fit for both parameters, where Δ(JES) is used for the in situ calibration of the jet energy scale. By applying a Feldman-Cousins approach, we establish an upper limit at 95% confidence level (CL) of Γ(t) <7.6 GeV and a two-sided 68% CL interval of 0.3 GeV <Γ(t) <4.4 GeV for a top-quark mass of 172.5 GeV/c(2), which are consistent with the standard model prediction.     

Internal Lewis acid assisted hydrogen bond donor catalysis

Boronate ureas are introduced as a new class of noncovalent catalysts for conjugate addition reactions with enhanced activity. Through intramolecular coordination of the urea functionality to a strategically placed Lewis acid, rate enhancements up to 10 times that of more conventional urea catalysts are observed. The tunable nature of boronate ureas is a particularly attractive feature and enables the rational design of catalysts for optimal performance, in terms of both activity and stereocontrol, in new bond-forming processes.     

OptiDock: virtual HTS of combinatorial libraries by efficient sampling of binding modes in product space

Products from combinatorial libraries generally share a common core structure that can be exploited to improve the efficiency of virtual high-throughput screening (vHTS). In general, it is more efficient to find a method that scales with the total number of reagents (Sigma growth) rather with the number of products (Pi growth). The OptiDock methodology described herein entails selecting a diverse but representative subset of compounds that span the structural space encompassed by the full library. These compounds are docked individually using the FlexX program (Rarey, M.; Kramer, B.; Lengauer, T.; Klebe, G. J. Mol. Biol. 1995, 251, 470-489) to define distinct docking modes in terms of reference placements for combinatorial core atoms. Thereafter, substituents in R-cores (consisting of the core structure substituted at a single variation site) are docked, keeping the core atoms fixed at the coordinates dictated by each reference placement. Interaction energies are calculated for each docked R-core with respect to the target protein, and energies for whole compounds are calculated by finding the reference core placement for which the sum of corresponding R-core energies is most negative. The use of diverse whole compounds to define binding modes is a key advantage of the protocol over other combinatorial docking programs. As a result, OptiDock returns better-scoring conformers than does serially applied FlexX. OptiDock is also better able to find a viable docked pose for each library member than are other combinatorial approaches.     

Structural features of organic anions: 7-Norbornadienyllithium

The structure of 7-norbornadienyllithium, a homoantiaromatic carbanion, is investigated with the semiempirical MNDO molecular orbital method. Alkene out-of-plane bendings persist even when the metal is fully solvated. The structural integrity of the monomer is retained in the dimer and solvated dimer; previously proposed dimers are inconsistent with lithium bonding and are not minimum energy structures on the MNDO hypersurface.