Epi-progoitrin, the major glucosinolate of Crambe abyssinica, was readily extracted from defatted crambe meal. A simple biotechnological process using immobilized myrosinase allowed a high-yielding chemo- and stereocontrolled transformation of epi-progoitrin into epi-goitrin, which was obtained in pure stereochemical form. Many diverse chemical modifications can be envisaged on the derived epi-goitrin which should be considered as a novel sophisticated starting material for the production of enantiomerically pure fine chemicals.