This combination provides improved yields and enantioselectivities with respect to the (S,S)-Mn(OTf)2( TIPS mcp)-acetic acid couple. As shown in Figure , the yields and enantioselectivities obtained in the desymmetrization of a series of monosubstituted cyclohexanes are strongly dependent on the nature of the substituent. Considering that substrate conformation may have an important role in determining the selectivity in asymmetric C-H oxidations, the substrate structure was subjected to conformational search followed by geometry optimization by DFT calculations to generate a library of over 130 molecular descriptors. Following the previously described workflow, the parameters derived from the most representative populated conformers at 233 K were extracted.