An Enantioselective CpxRh(III)‐Catalyzed C−H Functionalization/Ring‐Opening Route to Chiral Cyclopentenylamines

(cod) precatalyst and bis(o-toluoyl) peroxide as activating oxidant was developed for a C-H activation/ring-opening sequence between aryl ketoxime ethers and 2,3-diazabicyclo[2.2.1]hept-5-enes. This transformation provides access to densely functionalized chiral cyclopentenylamines in excellent yields and enantioselectivities of up to 97:3 er. The reported method is also well suitable for asymmetric alkenyl C-H functionalizations of α,β-unsaturated oxime ethers, furnishing skipped dienes with high levels of enantiocontrol.