Abstract:
There is enormous interest in the design and development of efficient chiral ligands for asymmetric
catalysis, as a result, this field has become one of the most popular areas of research in organic
chemistry. This project involved the investigation of the novel chiral pentacyclo-undecane (PCU)
diol 54a, PCU bisimine 87 and PCU bis(oxazoline) 100 type ligands. The PCU diol ligand was
synthesized, but proved to be difficult to obtain enantiomerically pure which hindered further
investigation into this type of ligand. The PCU bisimine ligand 87 was synthesized. However due
to its instability it was not further pursued. Synthesis of the PCU bis(oxazoline) ligand 100 was
successful. This ligand was complexed to various metal salts and its efficiency as a chiral Lewis
acid catalyst was evaluated on the asymmetric Diels-Alder reaction between 3-acryloyloxazolidin-
2-one 52 and cyclopentadiene 33. The anhydrous magnesium perchlorate ligand complex emerged
as the best catalyst providing the endo-cycloadduct product 53 in 81 % enantiomeric excess at -40
oC. Optimizations of the possible conformations of the magnesium complex of ligand 100 with the
substrate 52 were performed using Density Functional Theory (DFT) calculations. The more
energetically favoured complex conformation was established. The Re-face of the dienophile which
was less hindered produced the product consistent with the experimentally observed product 16.
Based on the calculated bond lengths from the computational model binding of the ether oxygen on
the PCU moiety to magnesium was observed. All the novel compounds were fully characterized
using NMR, IR and mass spectroscopy as the main tools.
