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.).     

Miscible blends of modified poly(aryl ether ketones) with aromatic polyimides

The phase behavior of binary blends of poly(ether ether ketone) (PEEK), sulfonated PEEK, and sulfamidated PEEK with aromatic polyimides is reported. PEEK was determined to be immiscible with a poly(amide imide) (TORLON 4000T). Blends of sulfonated and sulfamidated PEEK with this poly(amide imide), however, are reported here to be miscible in all proportions. Blends of sulfonated PEEK and a poly(ether imide) (ULTEM 1000) are also reported to be miscible. Spectroscopic investigations of the intermolecular interactions suggest that formation of electron donoracceptor complexes between the sulfonated/sulfamidated phenylene rings of the PEEKs and the n-phenylene units of the polyimides are responsible for this miscibility. © 1993 John Wiley & Sons, Inc.     

A dynamic finite volume scheme for large-eddy simulation on unstructured grids

In recent years there has been considerable progress in the application of large-eddy simulation (LES) to increasingly complex flow configurations. Nevertheless a lot of fundamental problems still need to be solved in order to apply LES in a reliable way to real engineering problems, where typically finite-volume codes on unstructured meshes are used. A self-adaptive discretisation scheme, in the context of an unstructured finite-volume flow solver, is investigated in the case of isotropic turbulence at infinite Reynolds number. The Smagorinsky and dynamic Smagorinsky sub-grid scale models are considered. A discrete interpolation filter is used for the dynamic model. It is one of the first applications of a filter based on the approach presented by Marsden et al. In this work, an original procedure to impose the filter shape through a specific selection process of the basic filters is also proposed. Satisfactory results are obtained using the self-adaptive scheme for implicit LES. When the scheme is coupled with the sub-grid scale models, the numerical dissipation is shown to be dominant over the sub-grid scale component. Nevertheless the effect of the sub-grid scale models appears to be important and beneficial, improving in particular the energy spectra. A test on fully developed channel flow at Re_τ = 395 is also performed, comparing the non-limited scheme with the self-adaptive scheme for implicit LES. Once again the introduction of the limiter proves to be beneficial.     

Topics in data assimilation: Stochastic processes

Stochastic models with varying degrees of complexity are increasingly widespread in the oceanic and atmospheric sciences. One application is data assimilation, i.e., the combination of model output with observations to form the best picture of the system under study. For any given quantity to be estimated, the relative weights of the model and the data will be adjusted according to estimated model and data error statistics, so implementation of any data assimilation scheme will require some assumption about errors, which are considered to be random. For dynamical models, some assumption about the evolution of errors will be needed. Stochastic models are also applied in studies of predictability.

The formal theory of stochastic processes was well developed in the last half of the twentieth century. One consequence of this theory is that methods of simulation of deterministic processes cannot be applied to random processes without some modification. In some cases the rules of ordinary calculus must be modified.

The formal theory was developed in terms of mathematical formalism that may be unfamiliar to many oceanic and atmospheric scientists. The purpose of this article is to provide an informal introduction to the relevant theory, and to point out those situations in which that theory must be applied in order to model random processes correctly.     

One-dimensional non-nearest-neighbor random walks in the presence of traps

A one-dimensional lattice random walk in the presence ofm equally spaced traps is considered. The step length distribution is a symmetric exponential. An explicit analytic expression is obtained for the probability that the random walk will be trapped at thejth trapping site.     

The Geometry of the Newton Method on Non-Compact Lie Groups

An important class of optimization problems involve minimizing a cost function on a Lie group. In the case where the Lie group is non-compact there is no natural choice of a Riemannian metric and it is not possible to apply recent results on the optimization of functions on Riemannian manifolds. In this paper the invariant structure of a Lie group is exploited to provide a strong interpretation of a Newton iteration on a general Lie group. The paper unifies several previous algorithms proposed in the literature in a single theoretical framework. Local asymptotic quadratic convergence is proved for the algorithms considered.     

Fluid and diffusion limits for transient sojourn times of processor sharing queues with time varying rates

We provide an approximate analysis of the transient sojourn time for a processor sharing queue with time varying arrival and service rates, where the load can vary over time, including periods of overload. Using the same asymptotic technique as uniform acceleration as demonstrated in [12] and [13], we obtain fluid and diffusion limits for the sojourn time of the M_t/M_t/1 processor-sharing queue. Our analysis is enabled by the introduction of a “virtual customer” which differs from the notion of a “tagged customer” in that the former has no effect on the processing time of the other customers in the system. Our analysis generalizes to non-exponential service and interarrival times, when the fluid and diffusion limits for the queueing process are known.     

Nonaqueous diazotization of 4-amino-3-arylisothiazole-5-carboxylate esters

4-Amino-3-arylisothiazole-5-carboxylate esters are converted to the corresponding desamino, chloro, bromo, and iodo esters by processes involving nonaqueous diazotization. These related procedures open up the possibility for the conversion of readily available heterocyclic ortho-amino esters and nitriles to related heterocyclic derivatives, which are not easily obtained by alternate routes.     

A short and efficient synthesis of grisan

A three-step synthesis of grisan (spiro[benzofuran-2(3H)-1′-cyclohexane]), using methoxymethoxybenzene and 1-chloromethylcyclohexene as starting materials, is described.