Enantiomerization of an inherently chiral resorcarene derivative: determination of the interconversion barrier by computer simulation of the dynamic HPLC experiment
Abstract The inherently chiral tetrabenzoxazine resorcarene derivative 1 shows characteristic plateau-formation during enantioselective HPLC separation on the chiral stationary phase Chiralpak AD. By computer assisted peak form analysis of the elution profiles, obtained from temperature dependent dynamic HPLC (DHPLC) experiments, with ChromWin, the enantiomerization barrier Δ G # (298 K)=92±2 kJ mol −1 and the activation parameters Δ H # =53.0±1.8 kJ mol −1 and Δ S # =−131±14 J (K mol) −1 were determined.
Chromatographically separable rotamers of an unhindered amide
Surprisingly stable formamide rotamers were encountered in the tetrahydroisoquinoline and morphinan series of alkaloids. We investigated the hindered rotation around the amide bond by dynamic high-performance liquid chromatography (DHPLC) and kinetic measurements of the interconversion of the rotamers which can readily be separated by HPLC as well as TLC. The experimental results of the different methods were compared to each other as well as to results obtained by DFT calculations.