Herein, we report an efficient synthetic method for constructing the tetracyclic scaffold of sulfur-containing discorhabdin-type alkaloids. The key to success is the BF•EtO-promoted dienone-phenol-type rearrangement/sulfur insertion cascade reaction, which converts the common and readily available -acetal-bridged tetracyclic framework to the labile and synthetically challenging -acetal-bridged tetracyclic framework in a single step. Additionally, the hypervalent iodine promoted intramolecular oxidative dearomatization terminated with amide and indium(III) acetate-facilitated radical cyclization were also essential elements in this study.
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