The versatility and utilization of phosphorus based compounds in classic carbon-carbon bond forming and esterification reactions

The phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) has been employed as an efficient reusable media for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts ofwater and toluene (single phase) using potassium phosphate and 1% Pd2(dba)3'CHCI3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and were all complete within 1 hour at 50°C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70°C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system, from which the catalyst was then recycled by removing the top (hexanes) and bottom (aqueous) layers and adding the reagents to the ionic liquid which was heated again at 50°C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences. IL ESTERIFICATIONREACTION A new class oftrialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence oftriethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and stenc nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.

Characterizing Dynamic Optimization Benchmarks for the Comparison of Multi-Modal Tracking Algorithms

Population-based metaheuristics, such as particle swarm optimization (PSO), have been employed to solve many real-world optimization problems. Although it is of- ten sufficient to find a single solution to these problems, there does exist those cases where identifying multiple, diverse solutions can be beneficial or even required. Some of these problems are further complicated by a change in their objective function over time. This type of optimization is referred to as dynamic, multi-modal optimization. Algorithms which exploit multiple optima in a search space are identified as niching algorithms. Although numerous dynamic, niching algorithms have been developed, their performance is often measured solely on their ability to find a single, global optimum. Furthermore, the comparisons often use synthetic benchmarks whose landscape characteristics are generally limited and unknown. This thesis provides a landscape analysis of the dynamic benchmark functions commonly developed for multi-modal optimization. The benchmark analysis results reveal that the mechanisms responsible for dynamism in the current dynamic bench- marks do not significantly affect landscape features, thus suggesting a lack of representation for problems whose landscape features vary over time. This analysis is used in a comparison of current niching algorithms to identify the effects that specific landscape features have on niching performance. Two performance metrics are proposed to measure both the scalability and accuracy of the niching algorithms. The algorithm comparison results demonstrate the algorithms best suited for a variety of dynamic environments. This comparison also examines each of the algorithms in terms of their niching behaviours and analyzing the range and trade-off between scalability and accuracy when tuning the algorithms respective parameters. These results contribute to the understanding of current niching techniques as well as the problem features that ultimately dictate their success.