Optically active synthetic and semisynthetic polymers were utilized as chiral stationary phases (CSPs) for the direct chromatographic enantioseparation of a series of 8-chloro-2,3-dihydro-3-methyl-1,2,5-benzothiadiazepin-4(5H)-one and thione 1,1-dioxide. Evaluation of stereochemical integrity of chiral analytes was assessed by enantioselective temperature and flow-dependent HPLC. A stopped-flow high-performance liquid chromatography (sfHPLC) procedure was developed for the determination of the rate constants and free energy barriers of enantiomerization of enantiomers of 8-chloro-2-(3-methylbut-2-enyl)-2,3-dihydro-3-methyl-1,2,5-benzothiadiazepin-4(5H)-thione 1,1-dioxide (compound 2) in the presence of Chiraspher and Chiralcel OD CSPs. In order to study the chiroptical properties of the individual enantiomers of analytes investigated, semipreparative chromatographic resolutions were performed. The assignment of the absolute configuration was empirically established by comparing the CD spectra of the separated enantiomers with those obtained from structural analogues.