Total Syntheses of Uncommon C 30 Terpenoids: Chamaecydin and Isochamaecydin.

(-)-Chamaecydin and (-)-isochamaecydin, two uncommon C 30 terpenoids comprising abietane-type diterpenes and thujane-type monoterpenes, were achieved from β-pinene with (-)-sabinene in 18 and 20 steps, respectively. Key steps include a Claisen-Ireland rearrangement to establish the all-carbon quaternary center, a Rh catalyzed C-H bond insertion reaction to install a spiro-five-membered ring and a Lewis acid promoted cyclization of polyenes to construct the two six-membered rings.