A new TiIII‐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 MeReO3‐catalyzed Rubottom oxidation, this approach has enabled the first total syntheses of rhodomolleins XX and XXII in 23 and 22 steps, respectively.

The first asymmetric total synthesis of (+)-jatrophalactam was reported, which unambiguously determined the absolute configuration of the titled natural product. The key features entail a conformationally controlled cyclopropanation, a Meldrum's acid adduct-engaged macrolactam formation, and a Pd(II)-mediated oxidative cyclization.

The first and asymmetric total syntheses of two C11-oxygenated hetisine-type diterpenoid alkaloids, namely, (+)-davisinol and (+)-18-benzoyldavisinol, is described. The concise synthetic approach features a HAT-initiated transannular redox radical cyclization, an ODI-Diels–Alder cycloaddition, and an acylative kinetic resolution. By incorporating an efficient late-stage assembly of the azabicycle, our strategy would streamline the synthetic design of C20-diterpenoid alkaloids and pave the way for their modular syntheses.

The first enantioselective total synthesis of (+)-alsmaphorazine E has been achieved through a traceless chirality transfer strategy, which also enabled structural reassignment of the natural product. Key features of this efficient approach entail a catalytic intramolecular oxidative cyclization, a diastereoselective oxidative cyclic aminal formation and a radical cyclization/transannular aza-Michael addition cascade.