Biomimetic Synthesis of Psiguajdianone Guided Discovery of the Meroterpenoids from Psidium guajava.

Psiguajdianone (1), a novel caryophyllene-derived meroterpenoid dimer, was isolated from Psidium guajava. The structure of 1 was determined by X-ray analysis and confirmed by total synthesis. Our synthetic strategy involves biomimetic cascade Knoevenagel condensation/hetero-Diels-Alder reaction and dimerization. Notably, the caryophyllene-derived meroterpenoids obtained during our synthesis were first identified as artifacts in the laboratory, and five of them were proven to be natural products present in the plant. Moreover, these compounds show significant anti-inflammatory activity.