Hydrodechlorination reaction of 3-(benzo-1,3-dioxol-5-yl)-3-chloro-2-methylacrylaldehyde in the presence of different low metal content heterogeneous mono- or bi-metallic catalysts was tested for the synthesis of the fragrance Helional® (3-[3,4-methylendioxyphenyl]-2-methyl-propionaldehyde). In particular, mono Pd/Al2O3, Rh/Al2O3 or bi-metallic Pd-Cu/Al2O3, Rh-Cu/Al2O3 catalysts were tested in different reaction conditions from which it emerged that mono-Rh/Al2O3 was the best performing catalyst allowing to achieve 100% substrate conversion and 99% selectivity towards Helional® in 24h at 80°C, p(H2) 1.0 MPa in the presence of a base. To establish correlations between atomic structure and catalytic activity, catalysts were characterized by Cu, Rh and Pd K-edge XANES, EXAFS analysis. These characterizations allowed to verify that the formation of Pd-Cu alloys and the presence of Cu oxide/hydroxide species on the surface of the Al2O3 support, are responsible for the very low catalytic efficiency of bimetallic species tested.