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In the first part, the use of chirality transfer in acyclic allylic systems was assessed for an intra- and an intermolecular reaction. The thermal [2,3] sigmatropic rearrangement of acyclic allylic phosphinites proved to be highly enantioselective, even at 110 °C and led to enantiomerically pure allylic phosphine oxides. The substitution pattern of the substrate and the reaction conditions were fully optimized.The chirality transfer concept was also used intermolecularly in asymmetric allylicdoi:10.5282/edoc.2541 fatcat:h4pk4o2x4rejrk467cwjjlpjqy