An Asymmetric Route to Xantholipin B, Prediction of Radical Reactions with Machine Learning, and Metal-Catalyzed Carbene Insertion into Aliphatic N−H Bonds

Throughout my time at UCI I have been involved in three projects: development of an asymmetric route to xantholipin B, asymmetric insertion of carbene groups into aliphatic N−H bonds, and developing a pedagogical training set for organic radical chemistry for prediction of reaction products and mechanistic pathways. In the Pronin group I optimized conditions for addition of a tri-n-butylstannylzinc reagent to a MOM-protected salicylaldehyde. In the Van Vranken group I synthesized and characterized a chiral guanidine catalyst useful for asymmetric catalysis. I then focused my efforts on the development of a prediction for prediction of step-wise organic reaction mechanisms based on machine learning. In order to improve the identification of electrophilic and nucleophilic atoms, I showed that easily calculated methyl ion affinities correlated with Mayr’s solution phase reactivity parameters, E and N•sN. I then helped to expand a training database of mechanistic radical reaction steps based on the SMIRKS formalism and test the system called Reaction Predictor once the training was complete

Preparation of Deuterium Labeled Compounds by Pd/C-Al-D2O Facilitated Selective H-D Exchange Reactions

The chemo/regioselective H-D exchange of amino acids and synthetic building blocks by an environmentally benign Pd/C-Al-D2O catalytic system is described. Due to the importance of isotope labeled compounds in medicinal chemistry and structural biology, notably their use as improved drug candidates and biological probes, the efficient and selective deuteration methods are of great interest. The approach is based on selective H-D exchange reactions where the deuterium source is simple D2O. D2 gas is generated in situ from the reaction of aluminum and D2O, while the commercially available palladium catalyst assists the H-D exchange reaction. The high selectivity and efficiency, as well as the simplicity and safe nature of the procedure make this method an environmentally benign alternative to current alternatives