Developing Comprehensive Computational Parameter Sets To Describe the Performance of Pyridine-Oxazoline and Related Ligands

The
applicability of computational descriptors extracted from metal
pyridine-oxazoline complexes to relate both site and enantioselectivity
to structural diversity was investigated. A group of computationally
derived features (e.g., metal NBO charges, steric descriptors, torsion
angles) were acquired for a library of pyridine-oxazoline ligands.
Correlation studies were employed to examine steric/electronic features
described by each descriptor, followed by application of the said
descriptors in modeling the results of two reaction types, the site-selective
redox-relay Heck reaction and the enantioselective Carroll rearrangement,
affording simple, well-validated models. Through experimental validation
and extrapolation, parameters derived from ground state metal complexes
were found to be advantageous over those from the free ligand.