It is interesting to compare the catalytic selectivity of DTBM-SEGPHOS for the cascade transformation of VPnone to that previously reported for monofunctional substrates bearing either the vinyl or the ketone function. It can be concluded from the literature that (S)-DTBM-SEGPHOS yields (S)-acetophenol (96% ee) and (R)-N,N-dibenzyl-1-phenylethan-1-amine (97% ee) from the HS of acetophenone and the HA of styrene, respectively. Therefore we expect the main isomer of the cascade reaction to be (S,R)-APnol. Simulated CD spectra from MM/MD optimized structure of (S,R)-APnol confirms that (S)-DTBM-SEGPHOS yields preferentially the stereoisomer with a (R) stereogenic center in  position of the amine (see the general methods in the SI). These observations not only establish the absolute and relative configurations of APnol but also further support that the ketone and vinyl functions of VPnone are transformed by the diphosphine Cu-H catalyst in an independent manner. Having established that VPnone is a suitable substrate to implement our concept, we next evaluated BTA helical catalysts for the same reaction. We selected BTA monomers and conditions that previously proved to be suitable for the coppercatalyzed HA of styrene (Scheme 1b): BTA P as achiral ligand with CF3 groups at the meta positions of the aryl moieties that were key for both activity and enantioselectivity, (S)-BTA as enantiopure monomer, and a-BTA as achiral additive that was found to be beneficial for both the yield and selectivity of the reaction. These monomers form helical terpolymers upon mixing in toluene, as schematically represented in Scheme 1b and previously characterized. The fraction of (S)-BTA (fs) over all BTA monomers was fixed to 20%, as it will allow to shift the handedness of the initial right-handed helices towards left-handed helices by adding a reasonable quantity of (R)-BTA monomers during the sequential transformation (vide infra). An excess of amine electrophile and silane was also found to enhance the yield. Similar to our previous work on the HA of styrene, catalytic screening was performed without exclusion of air. In this part, silane and amine transfer reagents are engaged from the beginning of the reaction, thereby enabling both HA and HS reactions to start concomitantly. With these initial conditions in hands, APnol is obtained in ca. 66% yield, 97% ee and a dr of 3.6:1 (Table , entry 1). The optical purity and handedness of the BTA helical coassemblies are controlled by the combined action of (S)-BTA and a-BTA; the achiral ligand coordinated to copper positioned in the righthanded homochiral helices provides (R,S)-APnol as the major stereoisomer. APnol is formed together with a small amount of EPnol (ca. 10%) and 3-vinylacetophenol (VPnol, 14%). The detection of VPnol but not of side products with unreacted ketone function indicates that HA is more challenging and occurs with a slower rate relatively to HS, a point confirmed by NMR monitoring of the concomitant process (Figure ). When (S)-BTA and (R)-BTA are engaged in equal amounts in the catalytic mixture, the resulting racemic helices furnish APnol as a virtually perfect equimolar mixture of its four stereoisomers, emphasizing the possibility to control the configurations of the two stereogenic centers by means of the handedness of the helical catalyst (Figure ). Concerning the influence of the nature of the amine electrophile, comparable catalytic performance is observed between 4-(((dibenzylamino)oxy)carbonyl)-N,N-dimethylaniline, an electron-rich amine transfer reagent commonly employed in Cu-H based processes, and Amine-tBu (Table , entry 2). The latter was selected for further screening given its higher solubility under our reaction conditions (toluene, 313 K). A set of tertiary phosphines was next evaluated as secondary ligands, a common strategy used to enhance the performance of Cu-H type catalysts (see Table for the full screening). Triphenylphosphine, electron-rich monophosphines and tested diphosphine ligands (dppe and dppbz) exhibit either no or detrimental effect. However, a slight but significant improvement in the yield in APnol, 76%, is observed upon addition of one equivalent of tris[3,5-bis(trifluoromethyl)phenyl]phosphine (P(3,5-(CF3)2-C6H3)3) relatively to copper (Table , entry 2). Other stoichiometries are less advantageous. Control experiment in Table , entry 3 confirms the important role played by a-BTA. Improved yield probably stems from a more homogeneous nature of the catalytic species when a-BTA is present in the supramolecular terpolymers. From the ee of the individual steps, it can also be seen that a-BTA significantly improves the ee of the HA reaction (compare ee2 in entries 2 and 3) but not of the HS step. The role of a-BTA in the BTA helical catalysts for the cascade reaction appears to be similar to that observed previously in the HA of styrene. The amount of a-BTA in the for more details. For entries 1-4, an internal standard is used to measure the yield in APnol on a crude sample whereas isolated yield is indicated for entries 5-6. The reactions on a 1 mmol scale are performed overnight. The enantiomeric excess and diastereomeric ratio are obtained from the chiral HPLC analyses of the crude (entries 1-4) or purified samples (entries 5-6). Error bars for ee and dr: see footnote of Table .