Transition-metal-mediated cascade reactions: the water-accelerated carboalumination-Claisen rearrangement-carbonyl addition reaction

[Chemical reaction: See text] A three-step cascade reaction involving a water-accelerated catalytic carboalumination, a Claisen rearrangement, and a nucleophilic carbonyl addition converts terminal alkynes and allyl vinyl ethers into allylic alcohols containing up to three contiguous asymmetric carbon centers. Stoichiometric quantities of water as an additive increase the rate of the [3,3] sigmatropic rearrangement as well as the diastereoselectivity of the carbonyl addition process. Reaction products contain 1,6-diene functionalities that are readily cyclized to substituted cyclopentenes. An extension of this methodology to a sequence involving a [1,3] sigmatropic shift was feasible with a cyclopropylmethyl vinyl ether substrate.     

A high-speed all-digital technique for cycle-resolved 2-D flow measurement and flow visualisation within SI engine cylinders

Particle image velocimetry (PIV) is now a well-established planar flow measurement technique for the study of in-cylinder flow fields in internal combustion engines. Here the authors describe a turnkey, high-speed digital imaging system that provides combined real-time flow visualisation and rapidly processed PIV data in an industrial optical research engine facility. The system is based on commercially available, high-speed imaging and laser technology and conventional digital cross-correlation processing to provide cycle-resolved PIV data and flow visualisation within timescales appropriate for engine development. A simple variation on the synchronisation scheme also allows the acquisition of tens to thousands of flow visualisation sequences and PIV maps at the same crank angle, thus giving the potential for the study of cycle-to-cycle flow variability and its effect on combustion stability in a suitably instrumented optical engine. The technique may also find applications in other unsteady or oscillatory flows of importance in aerodynamics, acoustics, mixing, and heat transfer.     

Variational Bayes and the Reduced Dependence Approximation for the Autologistic Model on an Irregular Grid With Applications

Discrete Markov random field models provide a natural framework for representing images or spatial datasets. They model the spatial association present while providing a convenient Markovian dependency structure and strong edge-preservation properties. However, parameter estimation for discrete Markov random field models is difficult due to the complex form of the associated normalizing constant for the likelihood function. For large lattices, the reduced dependence approximation to the normalizing constant is based on the concept of performing computationally efficient and feasible forward recursions on smaller sublattices, which are then suitably combined to estimate the constant for the entire lattice. We present an efficient computational extension of the forward recursion approach for the autologistic model to lattices that have an irregularly shaped boundary and that may contain regions with no data; these lattices are typical in applications. Consequently, we also extend the reduced dependence approximation to these scenarios, enabling us to implement a practical and efficient nonsimulation-based approach for spatial data analysis within the variational Bayesian framework. The methodology is illustrated through application to simulated data and example images. The online supplementary materials include our C++ source code for computing the approximate normalizing constant and simulation studies.     

Chemodivergence between Electrophiles in Cross-Coupling Reactions

Chemodivergent cross-couplings are those in which either one of two (or more) potentially reactive functional groups can be made to react based on choice of conditions. In particular, this review focuses on cross-couplings involving two different (pseudo)halides that can compete for the role of the electrophilic coupling partner. The discussion is primarily organized by pairs of electrophiles including chloride vs. triflate, bromide vs. triflate, chloride vs. tosylate, and halide vs. halide. Some common themes emerge regarding the origin of selectivity control. These include catalyst ligation state and solvent polarity or coordinating ability. However, in many cases, further systematic studies will be necessary to deconvolute the influences of metal identity, ligand, solvent, additives, nucleophilic coupling partner, and other factors on chemoselectivity.     

Rhodium‐Catalyzed Transnitrilation of Aryl Boronic Acids with Dimethylmalononitrile

An efficient transnitrilation of aryl boronic acids with dimethylmalononitrile (DMMN) is described. This rhodium‐catalyzed electrophilic cyanation presents a novel approach to prepare aryl nitriles by using a carbon‐bound cyanating reagent which undergoes cross‐coupling with the aryl boronic acid. The reaction expands the degree of functional‐group compatibility exhibited by the transnitrilation of aryl Grignard and aryllithium reagents. A variety of aryl boronic acid derivatives and dialkylmalononitriles were amenable to the transnitrilation.     

Preparation of certain 2-N-alkylamino-and 2-N,N-dialkylamino-10-methylphenothiazines via phenothiazyne

The treatment of 2-chloro-10-methylphenothiazine, 1 , with lithium alkylamide/alkylamine or lithium dialkylamide/dialkylamine yields the corresponding 2-N-alkylamino-or 2-N,N-dialkylaminophenothiazines in good yields via phenothiazyne. No significant reduction of 1 to 10-methylphenothiazine is observed. Yields of amines obtained by this method are considerably higher than those obtained by reacting 1 with sodamide in refluxing amine solvent. Attempts to introduce the -CH₂CN moiety onto the phenothiazine nucleus by treating 1 with sodamide and acetonitrile in liquid ammonia produced only 2-amino-10-methylphenothiazine.     

Practical stereoselective synthesis of an alpha-trifluoromethyl-alpha-alkyl epoxide via a diastereoselective trifluoromethylation reaction

A practical stereoselective synthesis is reported for an alpha-trifluoromethyl-alpha-alkyl epoxide (1), which is an important pharmaceutical intermediate. The key step involves a chiral auxiliary-controlled asymmetric trifluoromethylation reaction for the introduction of the unique trifluoromethyl-substituted tertiary alcohol stereogenic center in the target molecule. The fluoride-initiated CF3 addition to chiral keto ester 6a proceeded with a diastereoselectivity up to 86:14. The major diastereomer was readily obtained with a >99.5:0.5 dr through a simple crystallization of the crude product mixture.     

Biosorption of nickel in complex aqueous waste streams by cyanobacteria

A study was undertaken to determined if a suitable biosorbent could be found for removal of nickel at low concentrations (< 20 parts per million [ppm]) from a chemically complex wastewater effluent generated by electroplating operations. Algae and cyanobacteria were chosen as candidate biosorbent materials because they are easy to grow and they have the ability to withstand processing into biosorbent materials. Several species were screened for nickel-biosorption capacity initially, and three species of cyanobacteria were selected for further study based on their performance in the scoping tests. When compared to live controls, autoclaving improved the binding capacities of all three species, but usually biosorption data from experiments with live cells were more consistent. None of the three species was able to bind nickel efficiently in actual effluent samples. Further experimentation indicated that sodium ions, which were present in high concentrations in the effluent, were interfering with the ability of the cells to bind nickel. Adsorption isotherm plots for biosorption of nickel by two species ofAnabaena in NiCl₂-deionized water solutions were prepared. Managed by Martin Marietta Energy Systems, Inc., for the US Department of Energy under contract No. DEAC05-84OR21400.     

Phase Transfer Catalysis: Preparation of Alkyl Thiocyanates

Phase transfer catalysis has been employed for many nucleo-philic substitution reactions.¹ Generally these reactions have employed quaternary ammonium salts as catalysts. Among the displacement reactions reported is the formation of thiocyanates.² Tertiary amines have also been used as catalysts for phase transfer generation of carbenes.³ Recently we reported the preparation of alkyl cyanides to be catalyzed by amines under phase transfer conditions.⁴     

The proton magnetic resonance spectrum of β-propiolactone in two thermotropic nematic solvents

The molecule β-propiolactone has been studied in two thermotropic nematic solvents at 30·5°C. The proton magnetic resonance spectrum shows that the four protons are arranged in a plane with C _2v rather than D _2h symmetry. The interproton distance ratios are in reasonable agreement with the structure previously reported from a study of the rotational spectrum. These ratios are the same within experimental error in both thermotropic solvents reported here. Differences in line width and spectral quality are noted between the two solvents and this suggests that studies in more than one solvent are desirable to obtain the best analysis. The N.M.R. method is especially sensitive to extremely small changes in geometry reflected by the symmetry change D _2h to C _2v .