There is described a process for the manufacture of isoprene derivatives of the general formula ##STR1## wherein the asymmetric centres can each individually have the (R)- or (S)-configuration, R represents a residue of the formulae ##STR2## R.sup.1 signifies lower alkyl or both R.sup.1 's together signify ethylene or propylene and n stands for the number 0, 1 or 2, in which a compound, which is present in the (E)- or (Z)-form, of the general formula ##STR3## wherein R, n and an optionally present asymmetric centre have the above significance, is asymmetrically hydrogenated with a ruthenium complex of an optically active atropisomeric diphosphine.