Development of hydrogen-bonding catalysts for the kinetic resolution of amines via anion-binding

Methods development for chiral primary amine synthesis remains a challenge with efficient processes being quite limited. Outlined within this dissertation is the optimization of a bifunctional-hydrogen-bonding catalyzed aldol reaction between imides and aldehydes to produce highly enantioenriched β-hydroxy-α-amino acids. The main objective for the thesis work is the development of a new anion-binding approach for the kinetic resolution of amines. In the presence of an achiral nucleophilic co-catalyst, a chiral hydrogen-bonding catalyst, and benzoic anhydride, a chiral ion pair is presumably formed allowing for the efficient resolution of amines. The major challenges are outlined as well the successful extension to the resolution of benzylic amines. The work was further expanded to the more synthetically useful propargylic amines, while increasing the overall selectivities by designing and synthesizing a new chiral amide-thiourea catalyst for the study. Lastly, the more nucleophilic allylic amines were resolved in good selectivities by using PPY as the achiral co-catalyst.Ph. D.Includes bibliographical referencesIncludes vitaby Eric George Klaube