Rh-Catalyzed Enantioselective Allylation of <i>N</i>‑Tosyl- and <i>N</i>‑Nosylaldimines: Total Synthesis of (−)-Crispine A

The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of <i>N</i>-Ts- and <i>N</i>-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh­(I)/<b>L1b</b> catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (<i>E</i>)- and (<i>Z</i>)-crotyltrifluoroborate. Its synthetic utility is also illustrated in the total synthesis of (−)-crispine A