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The collective synthesis of skeletally diverse Stemona alkaloids featuring tailored dyotropic rearrangements of β‐lactones as key elements is described. Specifically, three typical 5/7/5 tricyclic skeletons associated with stemoamide, tuberostemospiroline and parvistemonine were first accessed through chemoselective dyotropic rearrangements of β‐lactones involving alkyl, hydrogen, and aryl migration, respectively. By the rational manipulation of substrate structures and reaction conditions, these dyotropic rearrangements proceeded with excellent efficiency, good chemoselectivity and high stereospecificity. Furthermore, several polycyclic Stemona alkaloids, including saxorumamide, isosaxorumamide, stemonine and bisdehydroneostemoninine, were obtained from the aforementioned tricyclic skeletons through late‐stage derivatizations. A novel visible‐light photoredox‐catalyzed formal [3+2] cycloaddition was also developed, which offers a valuable tool for accessing oxaspirobutenolide and related scaffolds.

We report a mild method for the synthesis of 4aH-carbazole intermediates with significant synthetic flexibility and variability, and demonstrate the controllable rearrangements of such intermediates to carbazoles. The work further...

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