title: Rhodium-catalyzed endo-selective epoxide-opening cascades: formal synthesis of (-)-brevisin.
abstract: [Rh(CO)2Cl]2 is as an effective catalyst for endo-selective cyclizations and cascades of epoxy-(E)-enoate alcohols, thus enabling the synthesis of oxepanes and oxepane-containing polyethers from di- and trisubstituted epoxides. Syntheses of the ABC and EF ring systems of (-)-brevisin via all endo-diepoxide-opening cascades using this method constitute a formal total synthesis and demonstrate the utility of this methodology in the context of the synthesis of marine ladder polyether natural products.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
authors.forename: Kurt W
authors.initials: KW
authors.lastname: Armbrust
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Beaver
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
authors.forename: Timothy F
authors.initials: TF
authors.lastname: Jamison
mesh_terms: D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry*; D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D004852:Epoxy Compounds; D004988:Ethers, Cyclic; D011083:Polycyclic Compounds; C550958:brevisin; D012238:Rhodium