CATALYST-CONTROLLED ALIPHATIC C-H OXIDATIONS

摘要

The invention provides simple small molecule, non-heme iron catalyst systems with broad substrate scope that can predictably enhance or overturn a Substrate Control Catalyst Control substrate's inherent reactivity preference for sp3-hybridized C—H bond oxidation. The invention also provides methods for selective aliphatic C—H bond oxidation. Furthermore, a structure-based catalyst reactivity model is disclosed that quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst. The catalyst systems can be used in combination with oxidants such as hydrogen peroxide to effect highly selective oxidations of unactivated sp3 C—H bonds over a broad range of substrates.

主权项

1. A composition comprising a complex of Formula (I): where X is a counterion; n is 2 or 3; L1 and L2 are ancillary ligands; each Z is independently H or CF3; R1, R2, R7 and R8 are each independently an alkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group; R3, R4, R5 and R6 are each independently hydrogen, halo, alkyl, heteroalkyl, aryl, and heteroaryl; and CA and NA, in combination with at least one pair of groups selected from the group consisting of R1 and R3, R1 and R4, R2 and R3, and R2 and R4, form at least one ring; and CB and NB, in combination with at least one pair of groups selected from the group consisting of R8 and R6, R8 and R5, R7 and R6, and R7 and R5, optionally form at least one ring.