NOVELTY - Preparation of landiolol hydrochloride with high enantiomeric excess, involves: reaction of (S)-(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3-(4-hydroxyphenyl)propanoate with oxirane compound, in presence of enantioselective catalyst containing metal bound to chelating ligand, to give substituted 2,2-dimethyl-(1,3)dioxolane compound (V) along with compound (IV) enriched in (S) isomer (XII); b) reaction of compound (V) in presence of base with N-(2-aminoethyl)morpholine-4-carboxamido)ethanamine or its salt to give landiolol; and c) salification of landiolol to give landiolol hydrochloride.    USE - For preparation of landiolol hydrochloride with high enantiomeric excess (claimed) useful as arrhythmic agent.    ADVANTAGE - The process is carried out without isolating most intermediates; and does not require chromatographic purifications and is advantageous in terms of yields and productivity. The resulting landiolol is pure and can be conveniently transformed into landiolol hydrochloride with high enantiomeric purity. The intermediate (V) is obtained with high purity in very high yields under very mild reactions conditions. The starting material epichlorohydrin, is very inexpensive and easily commercially available. The catalysts used are commercially available at low costs and can be easily recovered by simple filtration. The reaction to give landiolol starting from the (S)-(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3-(4-((2R)-3-chloro-2-hydroxy-propoxy)phenyl)propanoate (5a) provides a markedly higher yield than those obtained with most processes of the prior art. The resulting landiolol can be directly converted to landiolol hydrochloride in good overall yields, with no further purifications neither intermediate steps. The resulting landiolol hydrochloride has very high enantiomeric purity. The process allows to recover (S)-epichlorohydrin, which is a high added value product that can also be used in the synthesis of landiolol.    DETAILED DESCRIPTION - Preparation of landiolol hydrochloride with high enantiomeric excess, involves: a) reaction of (S)-(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3-(4-hydroxyphenyl)propanoate with substituted oxirane compound of formula (IV), in the presence of an enantioselective catalyst containing a metal bound to an enantiopure chelating ligand, to give substituted 2,2-dimethyl-(1,3)dioxolane compound of formula (V) along with the starting compound (IV) enriched in the (S) isomer (XII); b) reaction of the compound (V) obtained in step (a) in the presence of a base with N-(2-aminoethyl)morpholine-4-carboxamido)ethanamine as the free base or its salt to give landiolol; and c) salification of landiolol obtained in step b) to give landiolol hydrochloride.    X=halo or 1-3C alkylsulfonic or 6-10C arylsulfonic ester.    An INDEPENDENT CLAIM is included for new (S)-(2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3-(4-((2R)-3-chloro-2-hydroxy-propoxy)phenyl)propanoate (5a).