text: The Curtin–Hammett principle has been invoked to explain selectivity in a variety of synthetic pathways. One example is observed en route to the antitumor antibiotic AT2433-A1, in which a Mannich-type cyclization proceeds with excellent regioselectivity. Studies demonstrate that the cyclization step is irreversible in the solvent used to run the reaction, suggesting that Curtin–Hammett kinetics can explain the product selectivity.