ol8b00929_si_001.pdf (5.27 MB)
Aliphatic C–H Bond Oxidation with Hydrogen Peroxide Catalyzed by Manganese Complexes: Directing Selectivity through Torsional Effects
journal contribution
posted on 2018-04-20, 17:19 authored by Michela Milan, Massimo Bietti, Miquel CostasSubstituted N-cyclohexyl amides undergo aliphatic
C–H bond oxidation with H2O2 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.