Aliphatic C-H Bond Oxidation with Hydrogen Peroxide Catalyzed by Manganese Complexes: Directing Selectivity through Torsional Effects.

Substituted N-cyclohexyl amides undergo aliphatic C-H bond oxidation with HO catalyzed by manganese complexes. The reactions are directed by torsional effects leading to site-selective oxidation of cis-1,4-, trans-1,3-, and cis-1,2-cyclohexanediamides. The corresponding diastereoisomers are unreactive under the same conditions. Competitive oxidation of cis- trans mixtures of 4-substituted N-cyclohexylamides leads to quantitative conversion of the cis-isomers, allowing isolation and successive conversion of the trans-isomers into densely functionalized oxidation products with excellent site selectivity and good enantioselectivity.