In recent years the synthesis of amines and other nitrogen containing motifs has been a major area of research in organic chemistry due to their being widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a Pd-catalyzed oxidative amination reaction, where the addition of the nitrogen occurs at the less substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide via trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favored products. Both the scope of the transformation and mechanistic investigations are reported.

Nucleopalladation is one of the most common mechanisms for Pd-catalyzed hydro- and oxidative functionalization of alkenes. Due to the electronic bias of the π-alkene-palladium complexes, nucleopalladations with terminal aliphatic alkenes typically deliver the nucleophile to the more substituted sp2 carbon to form the Markovnikov-selective products. The selective formation of the anti-Markovnikov nucleopalladation products requires the inherent electronic effects to be overridden, which is still a significant challenge for reactions with simple aliphatic alkenes. Because the interactions between the nucleophile and the alkene substrate are influenced by a complex combination of multiple types of steric and electronic effects, a thorough understanding of the interplay of these underlying interactions is needed to rationalize and predict the regioselectivity. Here, we employ an energy decomposition approach to quantitatively separate the different types of nucleophile-substrate interactions, including steric, electrostatic, orbital interactions, and dispersion effects, and to predict the impacts of each factor on regioselectivity. We demonstrate the use of this approach on the origins of catalyst-controlled anti-Markovnikov-selectivity in Hull’s Pd-catalyzed oxidative amination reactions. In addition, we evaluated the regioselectivity in a series of nucleopalladation reactions with different neutral and anionic Pd catalysts and N- and O-nucleophiles with different steric and electronic properties. Based on these computational analyses, a generalized scheme is established to identify the dominant nucleophile-substrate interaction affecting the regioselectivity of nucleopalladations with different Pd catalysts and nucleophiles.

This thesis will analyze video from land-based, cooled mid-wave infrared cameras to identify temporal features indicative of a heat plume from a forest fire. Desirable features and methods will show an ability to distinguish between heat plume movement and other movements, such as foliage, vehicles, humans, and birds in flight. Features will be constructed primarily using combinations of statistics and principal component analysis (PCA) with intent to detect key characteristics of fire and heat plume: persistence and growth. Several classification systems will combine and filter the features in an attempt to classify pixels as either heat or non-heat. The classification systems will be tuned and compared with common metrics of error rate and computation time. It was found that the movement pattern of a heat plume could be distinguished from the similar movement pattern of foliage by detecting outlier movement patterns, a phenomenon associated with the growth property of fire. Outlier movement patterns were best detected by thresholding the quotient of mean and median of a set of variance measurements over time. The best tested classifier in terms of minimizing false positives without losing the heat signal came from PCA of a dual-range moving average difference.

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