To make this process successful, an enantioselective carboetherification step had to be developed. The reversible formation of the hemiaminal I from the propargylic amine prevents asymmetric induction at this stage (See SI, section E for more details). Therefore, a dynamic kinetic asymmetric transformation (DYKAT) needs to take place: in the presence of a chiral catalyst, one enantiomer of I should react preferentially to give oxazolidine II enantioselectively. Although palladium-catalyzed DYKATs have been reported, the envisaged process is highly challenging, due to the large distance between the chiral metal complex and the stereocenter. To the best of our knowledge, such DYKAT process has never been realized in the palladium-catalyzed functionalization of alkynes. If successful, the selection of the substitution pattern on the alkyne and on the aryl electrophile, together with the choice of the suitable enantiomer of the chiral ligand on the palladium catalyst would provide a simple enantio-and diastereodivergent access to all four stereoisomers of the amino alcohol. This is especially attractive for medicinal chemistry, as each stereoisomer may have different bioactivity, and the development of stereodivergent methods has been the topic of intensive research in asymmetric catalysis recently. We tested the feasibility of our plan by examining the palladium-catalyzed tethered carboetherification of the readily available propargylic amine 1 with iodotoluene 2 to access tetrasubstituted olefin 4 bearing a chiral oxazolidine fragment (Table ). 1-Ethoxy trifluoroethanol 3, a commercially available ethyl hemiacetal of trifluoroacetaldehyde, was chosen as the electrophilic molecular tether and Pd2(dba)3•CHCl3 as the palladium source. We first focused on the identification of a suitable ligand that could secure high level of stereoinduction in the process (for details, see SI, section C). Commonly used bidentate BINAP L1 and Josiphos ligands L2 and L3 were not competent for this reaction (entry 1). The P,N ligands L4 and L5, derived from the corresponding Ugi's amines, delivered 4 in moderate yield and enantiomeric excess (entries 2 and 3), nevertheless demonstrating that a DYKAT was possible. However, higher asymmetric induction could not be achieved with this class of ligands. The P,N ligand S-iPrPhox L6 yielded the desired product in 72% yield and 40% e.e. (entry 4). Promising results were obtained evaluating the Trost type ligands, commonly used for palladium catalyzed asymmetric allylation reactions. In particular, the commercially available DACH-phenyl Trost ligand L7 delivered product 4 in 49% yield and 64% e.e. (entry 5). Having in mind the previous positive results obtained with P,N ligands, we substituted the 2-(PPh2)-aryl fragment with a 2-pyridine. This change increased the e.e. to 74% (entry 6). Surprisingly, the best results were finally obtained employing the benzamide derived L9 lacking a second strongly coordinating site, which delivered quantitatively 4 with 90% e.e. (entry 7). To the best of our knowledge, ligand L9 has been reported only twice in the literature, and it was not suitable for imparting high stereocontrol, as two strong coordinating sites were required for asymmetric induction. We developed a robust and operationally simple route for accessing both enantiomers of L9 on multigram scale (SI, section B4). Demonstrating the process's robustness, the reaction could be performed in more "industrially preferred" solvents (ethyl acetate, methyl tert-butyl ether and toluene, entries 8, 9 and 10), without loss of yield and enantioselectivity, except for ethyl acetate (entry 8). Finally, the reaction could be scaled up to a 0.40 mmol scale, reducing the catalyst and ligand loading to 1.25 and 3.5 mol%, resulting in an improved stereoselectivity of 94% e.e. (entry 11). The structure of 4, obtained by X-ray single-crystal analysis (Scheme 2A), shows that the trifluoromethyl group is efficiently shielding one of the two enantiotopic faces of the olefin, setting the stage for the stereospecific hydrogenation. Indeed, when we submitted 4 to classical conditions for heterogeneous hydrogenation using Pearlman's catalyst, the desired hydrogenated product 5 was obtained as a single diastereoisomer in 79% yield and 94% e.e. (Scheme 2B). The use of Pearlman's catalyst also allowed simultaneous removal of the benzyl protecting group.