Reusable Selenenyl Iodide-Initiated Cascade Cyclization of Polyenes with N-terminating Groups

Although cascade cyclization of polyenes has advanced remarkably, most reported examples are limited to carbon- or oxygen-terminating groups, with nitrogen-terminating cyclizations remaining rare. In this work, we developed a cascade cyclization of polyenes with N-terminating groups, initiated by an isolable selenenyl iodide (RSeI) bearing a cavity-shaped substituent. Acid-labile substrates were successfully employed in the cascade cyclization. Compared with commonly used organoselenium reagents, a selenenyl iodide, characterized by its unique soft electrophilic nature, proved to be the most effective in promoting the cascade reaction. Furthermore, the stabilizing effect of the cavity-shaped substituent enabled the isolation of a selenenic acid (RSeOH), which was generated via oxidative β-selenoxide elimination from the cyclized product during its derivatization to an olefin, as a stable compound. We also developed a method for regenerating the starting selenenyl iodide from the selenenic acid. The reusability of the selenenyl iodide renders the series of molecular transformations environmentally benign by reducing unwanted organoselenium waste.