To demonstrate the synthetic utility of our method, some organic transformations to access unprecedented scaffolds were carried out (Scheme 4A). For example, the model enamide 2a was hydrogenated under simple Pd/C conditions at atmospheric pressure to obtain quantitative yields of 3a with high diastereoselectivity. Importantly, this method provides the anti-diastereomer predominantly, in contrast with our previous approach. Additionally, a Rh-catalyzed hydroboration protocol by Li and co-workers with an achiral ligand can be applied to arrive to a boron-containing compound 4a with three contiguous stereocenters. The pinacolborane moiety would provide another opportunity for other potential transformations. Next, alkylation to the respective tertiary enamide followed by a Au-catalyzed cyclization step, according to the conditions by Xu and co-workers, to gain access to the opposite diastereoisomer. The only example for a general E/Z isomerization protocol of enamides has been reported by Gooßen and co-workers through addition of Et3N at elevated temperatures to yield the thermodynamically favoured stereoisomer. However, this approach did not yield any noticeable E/Z isomerization for our system. Correspondingly, we established a novel protocol for the E/Z photoisomerization of iii. iv. One-pot 3-steps enamides in the presence of an Ir-photocatalyst and white LED. Under these conditions, it is possible to carry out an isomerization of the double bond to obtain the opposite diastereoisomer 6a with excellent inversion of the E/Z geometry. Control experiments prove that this reaction is indeed photocatalytic as both the photocatalyst and light are necessary. The E/Z isomerization could also be carried out in a one-pot three steps procedure starting directly from the 𝛼-chiral allylic amine 1a with or without prior evaporation of the solvent (Scheme 4B). Furthermore, a small scope was synthesized with diverse substituents and functional groups in different positions. In all cases, excellent inversion of the E/Z geometry alongside with high yields were obtained. Limitations were discovered to be 2s and 2y (see Supplementary Information). Importantly, the previously introduced 𝛾-chiral stereocenter is unaffected in all transformations.