Substituted 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.
Milan, M., Bietti, M., Costas, M. (2018). Aliphatic C−H Bond Oxidation with Hydrogen Peroxide Catalyzed by Manganese Complexes: Directing Selectivity through Torsional Effects. ORGANIC LETTERS, 20, 2720-2723 [10.1021/acs.orglett.8b00929].
Aliphatic C−H Bond Oxidation with Hydrogen Peroxide Catalyzed by Manganese Complexes: Directing Selectivity through Torsional Effects
Bietti, M.
;
2018-04-20
Abstract
Substituted 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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
