Controlling benzylic functionality and stereochemistry: 1. Synthesis of the secopseudopterosin aglycone

Directed, homogeneous hydrogenation of 1-(1-hydroxymethylethyl)-5-methoxy-3,4-dihydronaphthalene (7), followed by protection and selective benzylic oxidation gave the 1-oxo-(4R*, 11R*) compound (13). After addition of MeCeCl2, the natural C-1 stereochemistry was established by intramolecular hydride delivery from the di-t-butylsilylether. Final elaboration of the sidechain and the Ar ring substituents gave the secopseudopterosin aglycone other (3).