Asymmetric Total Synthesis of Fusarentin 6-Methyl Ether and Its Biomimetic Transformation into Fusarentin 6,7-Dimethyl Ether, 7-O-Demethylmonocerin, and (+)-Monocerin

Abstract

A concise asymmetric total synthesis of a fusarentin ether (1) with sequential biomimetic transformation to its analogues fusarentin 6,7-dimethyl ether (2), 7-O-demethylmonocerin (3), and (+)-monocerin (4) has been accomplished. The cis-fused furobenzopyranones of 7-O-demethylmonocerin (3) and (+)-monocerin (4) were efficiently constructed via an intramolecular nucleophilic trapping of a quinonemethide intermediate, which was obtained by benzylic oxidation of fusarentin 6-methyl ether (1) using hypervalent iodine reagent.