Finally, N-methyl, N-phenyl and N-paramethoxybenzyl (PMB) propargyl amines delivered products 33-35 52-58% yield and e.e.. The obtained enantioenriched tetrasubstituted olefins were then submitted to the optimized conditions for the diastereoselective hydrogenation (Scheme 4). Products 36-55 were all obtained as single diastereoisomers, confirming the robustness of our approach. Scale-up was straightforward and compound 5 could be obtained in 72% yield on 1.2 mmol scale without erosion of stereoselectivity. Heterocycles and functional groups containing coordinating N or S atoms and chlorides were not tolerated in the hydrogenation step (for details, see SI, Section D5). The nitrile and the carbonyl group within 25 and 27, were reduced to the corresponding amine 48 and alcohol 50. Interestingly, 5, 36, 45, 46, 47 and 54 are precursors of bioactive compounds with antidepressive activity, while the amino alcohols derived from 36 and 47 are intermediates for the synthesis of patented antiviral drugs candidates. Remarkably, our method provide high level of asymmetric induction even in the presence of sterically and electronically similar aryl substituents on the olefin, thus overcoming a common obstacle in the development of catalytic asymmetric reactions. Finally, to confirm the traceless nature of our strategy, we performed a mild acidic hydrolysis of the hemiaminal in 5. The enantioenriched amino alcohol 56 was obtained in 76% yield without loss in optical purity. We then demonstrated that this strategy provides a simple stereodivergent access to the four possible stereoisomers of chiral diaryl aminoalcohols by a judicious selection of the substrates and the ligands (Scheme 5). Starting from the benzyl propargyl amine 57, a sequence of i) Sonogashira coupling, ii) enantioselective carboetherification and iii) diastereoselective hydrogenation leads to all the stereoisomers of the desired products 5 and 36. Permuting the iodoarenes in the cross coupling and in the carboetherification steps allows the tuning of the E,Z geometry of the double bond. This selective process, combined with the choice of the enantiomer of the ligand, and the diasteroselectivity of the hydrogenation provides a selective access to the four stereoisomers of the diaryl amino alcohol precursors.