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Abstract The development of a convergent radical annulation strategy for the synthesis of complex terpenoids from sclareolide is disclosed. This approach employs a 1,3‐diradical synthon to enable rapid C‐ring annulation through inter‐ and intramolecular radical couplings, exemplified in the concise syntheses of serratene and cyclodammarane scaffolds from a common intermediate. Key features include a rapid alternating polarity (rAP) Kolbe electrolysis for onoceradiene assembly, a Co‐electrocatalytic metal‐catalyzed hydrogen atom transfer (MHAT) 7‐endo‐trig cycloisomerization─the first of its kind─to form the serratene core, and a tandem Fe‐mediated reductive olefin coupling/enolate alkylation cascade─also unprecedented─to forge the [4.3.1] propellane motif of cyclodammaranes with complete diastereocontrol over three contiguous quaternary centers. These routes, completed in 5–9 steps, maximize skeletal bond‐forming efficiency, feature unique radical cascades, and highlight the advantages of radical‐based disconnections in terpenoid synthesis. 

Electrochemical, fully stereoselective P(V)‐radical hydrophosphorylation of olefins and carbonyl compounds using a P(V) reagent is disclosed. By strategically selecting the anode material, radical reactivity is accessible for alkene hydrophosphorylation whereas a polar pathway operates for ketone hydrophosphorylation. The mechanistic intricacies of these chemoselective transformations were explored in‐depth. 

Abstract C−C linked glutarimide‐containing structures with direct utility in the preparation of cereblon‐based degraders (PROTACs, CELMoDs) can be assessed in a single step from inexpensive, commercial α‐bromoglutarimide through a unique Brønsted‐acid assisted Ni‐electrocatalytic approach. The reaction tolerates a broad array of functional groups that are historically problematic and can be applied to the simplified synthesis of dozens of known compounds that have only been procured through laborious, wasteful, multi‐step sequences. The reaction is scalable in both batch and flow and features a trivial procedure wherein the most time‐consuming aspect of reaction setup is weighing out the starting materials. 

Rapid alternating polarity greatly expands the functional compatibility of a venerable electrochemical carbon–carbon coupling.