Development of a magnesium (II) mediated intramolecular catalytic asymmetric alkylation

The reactions of enolates are some of the most basic transformations in organic chemistry. While there are limited examples of catalytic asymmetric enolate alkylations, many are restricted to specific acidic substrates or require preactivation of the enolate. As a starting point for the development of a more general method, we have begun to study intramolecular alkylations of epsilon-bromo oxazolidinone imides as a prelude to developing the more difficult intermolecular process. We have found that intramolecular alkylation takes place with soft enolizing bases in the presence of catalytic amounts of magnesium perchlorate and DBU. Importantly, the reaction is subject to ligand acceleration, particularly by Pybox type ligands, with enantioselectivities of up to 63%.;*Please refer to dissertation for diagrams.;Under catalytic conditions there were difficulties in obtaining a consistent reaction in terms of conversion of starting material to product. Once these obstacles are addressed an intramolecular catalytic asymmetric alkylation reaction can be reported.*...