Scheme 5. Combining trifunctional template 28 with Trp–Trp–Tyr rapidly forms complex polycycles. Initial amidation and Pictet–Spengler cyclization of Trp1 (i.e.29) followed by acid-promoted cyclization leads to macrocycle isomers 31a–f substituting the periphery of Trp2. Polycycle 31e results from indole C3 alkylation and cyclization to the endo-pyrroloindoline, analogously to related products obtained from template 1. *Note: peak 31d contained two product isomers that were not identified.