Solution Structures and Molecular Associations of a Peptide-Based Catalyst for the Stereoselective Baeyer–Villiger Oxidation

The
structural analysis of a peptide-based catalyst for the Baeyer–Villiger
oxidation (BVO) is reported. This unique structure is then analyzed
in the context of its previously documented facility to control selectivity
(both enantioselectivity and migratory aptitude) in catalytic reactions.
The effects of additives on the solution conformation of the peptide
are found to be dramatic, revealing substrate-specific interactions
and a possible “induced fit” model. The experimental
observation of dynamic behavior supports the notion that flexibility
in stereoselective catalysts can be an advantageous feature.