An Approach toward the Triquinane-Type Skeleton via Reagent-Controlled Skeletal Rearrangements. A Facile Method for Protection-Deprotection of Organomercurials, Tuning the Selectivity of Wagner-Meerwein Migrations, and a New Route to Annulated Lactones.

Abstract

Nonlinear triquinane-type building blocks have been synthesized using three strategic steps, namely, (1) Hg(2+)-mediated opening of a cyclopropane ring involving a skeletal rearrangement (3 --> 8), (2) an intramolecular organometallic addition across a C=O bond triggered by activation of the C-HgX group by means of Me(3)CuLi(2) (14 --> 26), and (3) selective, reagent-controlled skeletal rearrangements (43 --> 47 with Tl(3+) or Hg(2+); 43 --> 51 + 52 with Pd(2+); 44 --> 47 with Pd(2+)). A new method for protection/deprotection of organomercurials has been developed, which allows selective reduction of a carbonyl group with NaBH(4) and other hydrides (8 --> 14 --> 16 --> 20) and Tebbe methylenation (14 --> 31 --> 32). Oxidative demercuration (8 --> 11 + 28) and Pd(2+)-catalyzed carbonylation of organomercurials (20 --> 53) allowed syntheses of gamma- and delta-lactones.