Directed metalation/ligand coupling approach to the enantioselective synthesis of 1,1′-binaphthyls

Introduction of a 2-isopropoxycarbonyl or 2-NN-dimethylcarbamoyl group into homochiral 1-p-tolyl- or 1-t-butyl-sulfinylnaphthalenes, via directed metalation reaction, followed by ligand coupling reaction with 1-naphthylmagnesium bromide, furnished atropisomeric 1,1′-binaphthyls in 82–95% enantiomeric excess (e.e.).     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.     

Networks, Fields and Organizations: Micro-Dynamics, Scale and Cohesive Embeddings

Social action is situated in fields that are simultaneously composed of interpersonal ties and relations among organizations, which are both usefully characterized as social networks. We introduce a novel approach to distinguishing different network macro-structures in terms of cohesive subsets and their overlaps. We develop a vocabulary that relates different forms of network cohesion to field properties as opposed to organizational constraints on ties and structures. We illustrate differences in probabilistic attachment processes in network evolution that link on the one hand to organizational constraints versus field properties and to cohesive network topologies on the other. This allows us to identify a set of important new micro-macro linkages between local behavior in networks and global network properties. The analytic strategy thus puts in place a methodology for Predictive Social Cohesion theory to be developed and tested in the context of informal and formal organizations and organizational fields. We also show how organizations and fields combine at different scales of cohesive depth and cohesive breadth. Operational measures and results are illustrated for three organizational examples, and analysis of these cases suggests that different structures of cohesive subsets and overlaps may be predictive in organizational contexts and similarly for the larger fields in which they are embedded. Useful predictions may also be based on feedback from level of cohesion in the larger field back to organizations, conditioned on the level of multiconnectivity to the field.     

Magnetic-Field-Dependent Electronic Relaxation of Gd3+ in Aqueous Solutions of the Complexes [Gd(H2O)8]3+, [Gd(propane-1,3-diamine-N,N,N′,N′-tetraacetate)(H2O)2]−, and [Gd(N,N′-bis[(N-methylcarbamoyl)methyl]-3-azapentane-1,5-diamine-3,N,N′-triacetate)(H2O)] of interest in magnetic-resonance imaging

EPR Spectra have been measured for aqueous solutions of a series of Gd³⁺ complexes at variable temperature and a range of magnetic fields; S-band (0.14 T), X-band (0.34 T), Q-band (1.2 T), and 2-mm-band (5.0 T). The major contribution to the observed line widths is magnetic-field-dependent and is interpreted as being due to the modulation of the zero-field splitting produced by distortion of the complexes from perfect symmetry. The transverse and longitudinal relaxation matrices for an ⁸S ion with such an interaction have been calculated using Redfield theory with vector-coupling methods, and diagonalised numerically to obtain relaxation rates and intensities for the degenerate transitions which contribute to the multiplet. The observed line width, which is inversely proportional to the magnetic field at low temperatures, is best described by the intensity-weighted mean transverse relaxation time for the four transitions with non-zero intensity. A least-squares fit of the data yields the square of the zero-field splitting tensor, Δ², and a correlation time, τ_v, with activation energy, E_v. The physical significance of these parameters and the extent of validity of the theoretical approach are considered. The parameters are used to predict the magnetic-field dependence of the longitudinal and transverse electronic relaxation times, which are discussed in the context of their relevance to ¹H-NMR relaxivity.     

Some Fixed-Point Results for the Dynamic Assignment Problem

In previous work the authors consider the dynamic assignment problem, which involves solving sequences of assignment problems over time in the presence of uncertain information about the future. The algorithm proposed by the authors provides generally high-quality but non-optimal solutions. In this work, though, the authors prove that if the optimal solution to a dynamic assignment problem in one of two problem classes is unique, then the optimal solution is a fixed point under the algorithm.     

Improved experimental tracking techniques for validating discrete element method simulations of tumbling mills

We report on further developments in the three-dimensional tracking of a particle deep within the tumbling ball charge of an experimental mill. The experimental X-ray program employing the use of bi-planar X-ray angiography now includes the tracking of a typical 6 mm bulk charge particle in three dimensions with a spatial resolution that is accurate to within 0.15 mm. The improved experimental tracking techniques presented were developed for the purpose of generating accurate three-dimensional particle trajectory data against which to validate a numerical method for the simulation of discrete media, namely the discrete element method (DEM). These improvements are complimented with techniques for comparing charge profiles between numerical DEM simulations and three-dimensional experimental trajectory data.