Micranthanone A, a new diterpene with an unprecedented carbon skeleton from Rhododendron micranthum.

A new diterpene with an unprecedented carbon skeleton, micranthanone A (1), two new grayanane diterpenoids bearing an unusual 5,6-(3,4-dihydroxylbenzylidene acetal) motif, rhodomicranols A (2) and B (3), and three known grayanane diterpenoids (4-6) were isolated from Rhododendron micranthum. Their structures were elucidated by spectroscopic analyses, calculated ECD, and single-crystal X-ray diffraction. The in vitro immunomodulatory activities of 1-6 were evaluated, and a plausible biogenetic pathway for 1 is proposed.