Exploratory studies aimed at a synthesis of vinigrol. 2. Attempts to exploit ring-closing metathesis for construction of the central cyclooctane belt.

A program directed to the possible adaptation of ring closing metathesis to a total synthesis of vinigrol is described. With a convenient route to intermediates of general type 3 available from a prior investigation, several candidate substrates were prepared. These included the epoxy dienes 10 and 22, the diacetoxy triene 42, and the heavily functionalized cyclohexane 48. The central issue of this approach was to convey a maximum degree of conformational flexibility to these functionalized intermediates, such that the olefinic termini of the side chains could enter into intramolecular carbon−carbon bond formation. In no example was ring closure observed to operate. Instead, the strategically placed π-bonds were seen to migrate internally to the chain in select examples. Although the pivotal transformations failed, the deployment of a number of useful stereocontrolled reactions has ultimately resulted in the preparation of heavily substituted cis-decalins.