Classical kinetic theory of gases is based on the Boltzmann equation (BE) which describes the evolution of a system of particles undergoing collisions preserving mass, momentum and energy. Discretization methods have been developed on the idea of replacing the original BE by a finite set of nonlinear hyperbolic PDEs corresponding to the densities linked to a suitable finite set of velocities. One open problem related to the discrete BE is the construction of normal (fulfilling only physical conservation laws) discrete velocity models (DVMs). In many papers on DVMs, authors postulate from the beginning that a finite velocity space with such "good" properties is given, and after this step, they study the discrete BE. Our aim is not to study the equations for DVMs, but to discuss all possible choices of finite phase spaces (sets) satisfying this type of "good" restrictions. We start by introducing the most general class of discrete kinetic models (DKMs) and then, develop a general method for the construction and classification of normal DKMs. We apply this method in the particular cases of DVMs of the inelastic BE (where we show that all normal models can be explicitly described) and elastic BE (where we give a complete classification of normal models up to 9 velocities). Using our general approach to DKMs and our results on normal DVMs for a single gas, we develop a method for the construction of the most natural (from physical point of view) subclass of normal DVMs for binary gas mixtures. We call such models supernormal models (SNMs). We apply this method and obtain SNMs with up to 20 velocities and their spectrum of mass ratio. Finally, we develop a new method that can lead, by symmetric transformations, from a given normal DVM to extended normal DVMs. Many new normal models can be constructed in this way, and we give some examples to illustrate this.

The research described in this thesis focuses on the catalytic acylative kinetic resolution (KR) of aromatic secondary alcohols, using a planar-chiral 4-(dimethylamino)pyridine (DMAP) organocatalyst. In the first part of this thesis, the substrate scope of the above mentioned process was expanded to aromatic secondary alcohols that contain an extra functional group in the alkyl moiety, such as 1,2-azido alcohols, 2-hydroxy-2-aryl-ethylphosphonates and 2-hydroxy-2-aryl esters. Thus, the preparation of highly functionalized compounds in their enantiomerically pure form with excellent enantiomeric excess (up to 99% ee) was achieved. Furthermore, the synthetic applicability of this methodology was illustrated through the synthesis of two high value compounds, (R)-Pronethalol and (S)-3-hydroxy-N-methyl-3-phenylpropanamide, which is an immediate precursor of bioactive molecules such as (S)-Fluoxetine. The second part of this thesis deals with the mechanistic study of the acylative KR catalyzed by the planar-chiral DMAP derivative. Reaction Progress Kinetic Analysis methodology was used in the investigation of the reaction mechanism, probing that no notable product inhibition or decomposition of the catalyst occurs in the studied system. The reaction rate showed fractional order dependence on the concentration of both reactants. Furthermore, NMR spectroscopy was utilized to study the equilibrium between the different catalyst states, which explains the measured kinetics of the reaction.

No description available.

No description available.

No description available.

No description available.

Thesis advisor: Marc L. Snapper / Chapter 1: Brief overview of the catalytic enantioselective functionalization and kinetic resolution of alcohols Chapter 2: Kinetic resolution of syn-diols by catalytic enantioselective sulfonylation Chapter 3: Significant improvement on catalytic enantioselective silylation of syn-diols and triols through the use of a tetrazole additive / Thesis (MS) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

archives@tulane.edu / 1 / Joris P Lindhout

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2006. / Includes bibliographical references (leaves 128-136). Also available in electronic version.

Detailed mechanistic studies were conducted on several organic reactions that exhibit product selectivity (regio-, peri-, or enantioselectivity). The organic reactions studied were electrophilic aromatic substitutions, Diels-Alder cycloadditions of 1,3- dienes with cyclopentadieneone, Lewis acid catalyzed ene reactions with olefins, chlorinations of alkynes, and the enantioselective intramolecular Stetter reaction. Analyses of these systems were conducted by measurement of kinetic isotope effects, standard theoretical calculations, and in some cases dynamic trajectories. Mechanistic studies of electrophilic aromatic substitution, Lewis acid catalyzed ene reaction with olefins, the chlorination of alkynes, and the Diels-Alder cycloadditions of 1,3-dienes with cyclopentadienones, suggest that the origin of selectivity is not always a result of selectivity result from a kinetic competition between two closely related pathways to form distinct products. All of these systems involve one transition state on a potential energy surface that bifurcates and leads to two distinct products. In these systems, experimental kinetic isotope effects measured using natural abundance methodology, theoretical modeling of the potential energy surfaces, and trajectory analyses suggests that selectivites (regio- and periselectivities) are a result of influences by momenta and steepest-descent paths on the energy surface. The work here has shown that in order to understand selectivity on bifurcating surfaces, transition state theory is not applicable. In place of transition state energetics, the guiding principles must be those of Newtonian dynamics. In the mechanistic studies for the enantioselective intramolecular Stetter reaction, the origin of selectivity is a result of multiple transition states and their relative energies. Experimental H/D kinetic isotopes effects had lead to the conclusion that two different mechanisms were operating for reactions where carbenes were generated in situ versus reactions using free carbenes. However, 13C kinetic isotope effects and theoretical modeling of the reaction profile provide evidence for one mechanism operating in both cases.