A non‐oxidant and metal‐free strategy for synthesizing iso‐coumarin by using a continuous electrochemical microreactor to initiate an oxidative cyclization reaction of o‐(1‐alkynyl) benzoate and radicals. This efficient and clean continuous electrosynthesis method not only avoids the complicated gas protection operation and production of by‐products in the batch processes, but also help to overcome the difficulty that batch metal catalysis and electrocatalysis are difficult to scale up, and has the potential for pilot‐scale experiment.

The concise and divergent total synthesis of (−)‐indoxamycins A, C, and F has been completed for the first time by using a tricyclic enone as the common late‐stage intermediate. The key steps of the strategy are based on an Ireland–Claisen rearrangement, a stereodivergent reductive 1,6‐enyne cyclization, and a tandem 1,2‐addition/oxa‐Michael/methylenation reaction.

A concise and efficient approach for the diastereoselective total synthesis of salvileucalin C, as well as their biosynthetically related diterpenoids salvileucalin D, salvipuberulin, isosalvipuberulin, and dugesin B, has been reported for the first time. The key features of the strategy are based on a Beckwith-Dowd ring expansion, a tandem diastereoselective Stille coupling/debromination/desilylation/lactonization reaction, and a photoinduced electrocyclic ring contraction.

A concise total synthesis of rac-alsmaphorazine D has been described for the first time. The efficient synthetic strategy features four key transformations: 1) a catalytic intramolecular oxidative cyclization for the δ-lactamindole backbone; 2) an oxidative cyclic aminal formation for the hexahydropyrrolo[2,3-b]pyrrole framework; 3) a transannular radical cyclization for the construction of the diazabicyclo[3.3.1]nonane structure; and 4) a one-pot desilylation/double epimerization reaction that affirms the relative stereochemistry.

Here we describe the use of the hexadehydro-Diels–Alder (HDDA) reaction for the de novo construction of the isoindolinone scaffold and its application to the synthesis of the title natural products. The key isoindolinone-forming HDDA reaction involved an unprecedented substrate motif in which an amide carbonyl group was conjugated to the 4π 1,3-diyne component. In addition, a dimethylsilyl (−SiMe2H) substituent was exploited to trigger a Fleming–Tamao–Kumada oxidation for the installation of an essential phenolic hydroxyl group.