Total synthesis of natural p-quinol cochinchinenone.

Cochinchinenone has been synthesized in only five steps and four pots and in 58% overall yield from commercially available 2,3-dimethoxy-4-hydroxy-benzaldehyde and OPMB-protected p-hydroxy acetophenone, the key step being the oxone-mediated oxidative dearomatization of the corresponding ketone-containing p-substituted phenol.

Direct stereocontrolled synthesis of polyoxygenated hydrobenzofurans and hydrobenzopyrans from p-peroxy quinols.

An acidic-basic tandem catalytic process on p-peroxy quinols with hydroxy alkyl chains at C-4 allowed the one-pot synthesis of hydrobenzofuran and hydrobenzopyran tricyclic epoxides. In this transformation, two new cycles and four new stereogenic centers are created in a highly stereocontrolled manner. The usefulness of the strategy is illustrated with the first total synthesis and structural revision of natural product Cleroindicin D.