ASYMMETRIC, STEREOCONTROLLED TOTAL SYNTHESIS OF (-)-BREVIANAMIDE-B

The asymmetric, stereocontrolled total synthesis of (-)-brevianamide B(2) is described. The synthesis features a stereocontrolled intramolecular SN2' cyclization to construct the central bicyclo[2.2.2] nucleus. A synthetic route to C-10-epibrevianamide A (49) is also described. A synthetic sample of a shunt metabolite (9) proposed by Birch in 1972 has been prepared and its oxidation chemistry in the context of the proposed biosynthetic schemes is discussed. © 1990, American Chemical Society. All rights reserved.