Kinetic resolution of several tertiary alcohols has been evaluated with a peptide-based catalyst that was designed to probe the role of dihedral angle restrictions for certain bonds within the catalyst. In particular, the nucleophilic residue (π-Me)–His has been replaced with the (β-Me)–(π-Me)–His. A synthesis of the key residue is presented, along with characterization data that suggests the substituent exerts a substantial ground state conformational effect. In addition, kinetic resolution data indicate that the H- to Me-substitution confers enhanced stereoselectivity in several tertiary alcohol resolutions.