Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C−O Bond Formation

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.     

Element Pools and Numeric Coprocessors for Linear Programming on Personal Computers

This note discusses the need to use various data-compaction schemes in the implementation of sophisticated large-scale linear programming codes on modest personal computers. It demonstrates a method whereby the overhead of using these schemes is significantly reduced on Intel 80 x 86 processors.     

Experiments in Solving Mixed Integer Programming Problems on a Small Array of Transputers

The time-consuming process of solving large-scale Mixed Integer Programming problems using the branch-and-bound technique can be speeded up by introducing a degree of parallelism into the basic algorithm. This paper describes the development and implementation of a parallel branch-and-bound algorithm created by adapting a commercial MIP solver. Inherent in the design of this software are certain ad hoc methods, the use of which are necessary in the effective solution of real problems. The extent to which these ad hoc methods can successfully be transferred to a parallel environment, in this case an array of at most nine transputers, is discussed. Computational results on a variety of real integer programming problems are reported.     

Palladium‐Catalysed Cross‐Coupling of Vinyldisiloxanes with Benzylic and Allylic Halides and Sulfonates

The Hiyama cross‐coupling reaction is a powerful method for carbon–carbon bond formation. To date, the substrate scope of this reaction has predominantly been limited to sp²–sp² coupling reactions. Herein, the palladium‐catalysed Hiyama type cross‐coupling of vinyldisiloxanes with benzylic and allylic bromides, chlorides, tosylates and mesylates is reported. A wide variety of functional groups were tolerated, and the synthetic utility of the methodology was exemplified through the efficient total synthesis of the cytotoxic natural product bussealin A. In addition, the antiproliferative ability of bussealin A was evaluated in two cancer‐cell lines.     

Some Lessons in Solving Practical Integer Programs

Integer programs are harder to solve than linear programs of similar size. Even those of modest size may prove sufficiently difficult to deter practitioners from using them. But, formulated with care and solved with an appropriate branching strategy, they may be solved quickly. This paper discusses the elements of good formulation, high level branching constructs and effective branching strategies. These methods are applied to four practical case studies which are explored in depth.     

Using Control Variables to Improve the Efficiency of Percentile Estimation in Stochastic Simulation

Control variables may be used in the estimation of percentiles by stochastic stimulation. Hitherto control variables have only been applied to estimating the mean of a response variable; however, in many uses of simulation, information about the tails of the distribution of a response variable are of more interest. The efficacy of the method is demonstrated by application to an example of a simulation study in capital budgeting where exposure to risk is important.     

Self-Assembled Bilayers on Indium-Tin Oxide (SAB-ITO) Electrodes: A Design for Chromophore-Catalyst Photoanodes

A novel approach for creating assemblies on metal oxide surfaces via the addition of a catalyst overlayer on a chomophore monolayer derivatized surface is described. It is based on the sequential self-assembly of a chromophore, [Ru(bpy)(4,4'-(PO(3)H(2)bpy)(2))](2+), and oxidation catalyst, [Ru(bpy)(P(2)Mebim(2)py)OH(2)](2+), pair, resulting in a spatially separated chromophore-catalyst assembly.     

New process for the preparation of methyl carbonates

The methyl carbonate of HOBt was developed for the conversion of alcohols to carbonates. This method is superior to the use of methyl chloroformate or methyl pyrocarbonate, especially with more hindered alcohols. The reagent is a stable solid that is easily prepared on a multigram scale. [reaction: see text]