With highly selective, asymmetric intermolecular TDO cycloadditions established, we turned to enantioselective syntheses of the Strychnos alkaloids. We first explored the asymmetric variant of the intramolecular (tethered) cascade already established for the racemic synthesis of akuammicine (see Fig. ); a key issue was whether the excellent stereocontrol imparted by the camphorsultam group for the intermolecular cycloadditions would be maintained in an intramolecular setting. To our delight (Fig. ), treatment of the N-alkylated tryptamine 9 with TDO 14a under equivalent conditions to those employed previously (r.t. to 80 °C) afforded a single diastereoisomer of the IEDDA cycloadduct; this intermediate dienamine was also reduced in situ to afford two isomers 16 and 16' in a 1:1.4 ratio (see Supplementary Table for details) and 68% overall yield from 14a.