title: A Formal Enantiospecific Synthesis of 7,20-Diisocyanoadociane.
abstract: 7,20-Diisocyanoadociane (DICA) is a potent antimalarial isocyanoterpene endowed with a fascinating tetracyclic structure composed of fused chair cyclohexanes. We report a highly stereocontrolled synthesis of a late-stage intermediate, the "Corey dione", from which DICA has been made previously. This formal synthesis features a rapid buildup of much of the complexity of the target through a sequence of enone tandem vicinal difunctionalization, Friedel-Crafts cyclodehydration, and sequential stereocontrolled reductions. Most importantly, this success establishes the broader feasibility of our previously developed general synthesis approach to the isocyanoterpene family and provides a blueprint for a very direct synthesis of DICA and related natural products.
authors.affiliation: Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, Irvine, CA, 92697-2025, USA.
authors.forename: Philipp C
authors.initials: PC
authors.lastname: Roosen
authors.affiliation: Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, Irvine, CA, 92697-2025, USA. cdv@uci.edu.
authors.forename: Christopher D
authors.identifier: 0000-0001-7218-4521
authors.initials: CD
authors.lastname: Vanderwal
keywords: chiral pool; isocyanoterpenes; natural products; stereocontrol; total synthesis