Synthetic studies toward the kempane diterpenes. Construction of a key tricyclic intermediate

Abstract

A synthetic sequence is described for construction of the tricyclic portion (35) of kempane diterpenes. The central stereochemistry was established by a Diels-Alder addition of 2,6-dimethyl-para-benzoquinone to a 5-membered, dithiane-protected diene, and the addition of acetylide, with very high chemoselectivity, provided a suitably functionalized handle that will be incorporated into the final seven-membered ring. The remaining stereogenic centres about the decalin moiety were established by a series of equilibration and reduction steps.