Total Syntheses of Rhodomolleins XX and XXII: A Reductive Epoxide‐Opening/Beckwith–Dowd Approach

A new Ti III ‐mediated reductive epoxide‐opening/ Beckwith–Dowd rearrangement process efficiently assembles the bicyclo[3.2.1]octane framework of highly oxidized grayanane diterpenoids. By incorporation of a Cu(tbs) 2 ‐catalyzed (tbs= N ‐ tert ‐butylsalicylaldiminato) intramolecular cyclopropanation, a diastereoselective oxidative dearomatization‐induced Diels–Alder cycloaddition and a MeReO 3 ‐catalyzed Rubottom oxidation, this approach has enabled the first total syntheses of rhodomolleins XX and XXII in 23 and 22 steps, respectively.