Asymmetric Total Synthesis of (-)-Maldoxin, a Common Biosynthetic Ancestor of the Chloropupukeananin Family.

The total synthesis of pestheic acid based on an intramolecular SNAr reaction without a nitro group and the asymmetric synthesis of (-)-maldoxin by a catalytic enantioselective oxidative dearomatization of pestheic acid are described. The reactivity of (-)-maldoxin as a diene in the Diels-Alder reaction is also investigated.