Figure 26.
Development of a predictive, quantitative model for site-selective aliphatic C-H oxidations with Fe(PDP) and Fe(CF3-PDP). (A) Parameterization of electronic, steric, and stereoelectronics properties of C-H bonds enables development of a site-filter that identifies likely sites for oxidation with PDP catalysts that are remote from existing functionality, relatively unhindered, and stereoelectronically activated. (B) Development of a predictive model entails mathematically correlating the substrate properties with the empirically observed site-selectivities as a function of catalyst. (C) Predicted site-selectivity on a nectaryl derivative. (D) Predicted site-selectivity on a finasteride derivative. (E) A linear correlation was found between the predicted and observed site-selectivities as a function of catalyst. Panels B/E: Reproduced with permission from ref 13. Copyright 2013 ACS.